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CHIMIE ANORGANICA GENERALA SI APLICATA

Profesor universitar dr. chim. Ana Emandi










Chimia si chimismul reprezinta de fapt comportamentul invelisului electronic al unui atom







Prefata

I. Introducere
II. Cuprins

1
. CUNOSTINTE DE BAZA
-
elemente chimice

-
valente

-
Nnumar de oxidare

-
tipuri de reactii

-
tipuri de compusi
2
.
trecerea
de la
general
la
particular
pe grupe si blocuri de
elemente
3
.
DEZVOLTAREA

RELATIEI
Structura proprietati
structura, date termochimice
date cinetice.
4
. Chimia Aplicata la
Sursele alternative de
energie
5
. Chimia aplicata in
Restaurare / Conservare
CHIMIA
ANORGANICA
1
.
1
Operatii de Baza
in lABORATOR
-
solutii
-
solventi
-
cinetica, termochimie
-
sinteze
-
verificarea unei structuri prin
metode chimice si fizice
-
separari
-
purificari
echivalenti chimici

Introducere in chimia nemetalelor

Nemetalele sunt elemente chimice care ocupa in sistemul periodic blocul p grupele 13, 14, 15, 16, 17, 18;

Sistemul Periodic ( simboluri, velente, configuratii electronice, variatia proprietatilor fizice si chimice)
H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uuo
Uue Ubn
Alkali metals
Alkaline earth
metals
Lanthanoids Actinoids
Transition
metals
Other metals Metalloids
Other
nonmetals
Halogens Noble gases











Prezentarea generala a nemetalelor
GRUPA VII / 17


GRUPA VI / 16

Oxygen lichid sulful seleniul





GRUPA V /15

Azot fosfor arseniu stibiu bismut

GRUPA IV/14

carbon-diamant carbon grafit Siliciu germanium staniu


MATERIA (Ocupa spatiu si are o greutate) = mai multe materiale

Materialul = mai multi compusi chimici si/sau elemente


Elemente compusi (anorganici si organici )
Elementul este o substanta chimica este o combinatie chimica
care nu mai poate fi descompusa ce contine doua sau mai
in alte substante mai simple prin multe elemente chimice.
metode chime commune.
!! Izotopi, atom gram, molecula gram, molul molecula gram, masa moleculara, molul
Metale Nemetale / Metaloizi Clase de compusi anorganici Clase de comp.org
- solide (Hg) - prezinta toate starile de agregare (Br) - oxizi - hidrocarburi
- conduc electricitatea si caldura - nu conduc electricitatea si caldura - baze - comp. cu functiuni simple
- sunt lucioase si netransparente - transparenta moderata, unele au luciu - acizi - comp. cu funct mixte
- maleabile si ductile - nu sunt ductile si malleabile - saruri - comp. heterociclici
- coloranti
- compusi naturali
( rasimi, zaharide, proteine )
Compusii chimici sunt caracterizati de energie de legatura,
legatura chimica, structura cristallina, cinetica chimica,
constante fizico-chimice
Proprietatile materiei
fizice chimice
culoare sulful este galben
miros amoniacul are miros intepator
- gust zaharul este dulce
- greutate specifica Pb este greu, Al este usor
- conductibilitate electrica Cu
- conductibilitate termica Al
- punct de topire diamantul foarte ridicat
- rezistenta la intindere Fe si otelul
- ductilitatea Ag
maleabilitatea Au
- rezistenta la incalzire CaO stabil, HgO se
descompune
- reactivitatea chimica in contact cu alte substante
Fe rugineste








Modificari ale materiei
Fizice chimice
- se modifica numai proprietatile fizice - se modifica total substanta si se formeaza alta noua
- compozitia ramane aceeasi prin reactie chimica
- ex: inghetarea apei, ruperea sticlei, macinarea zaharului - arderea benzinei, fermentatia fructelor, ruginirea Fe













TIPURI DE REACTII CHIMICE IN CHIMIA ANORGANICA

I. Reactii chimice fara modificarea starii de oxidare ( de urmatoarele tipuri)
Acid/Baza NaOH + HCl NaCl + H
2
O
Precipitare/Solubilizare (reactii de deplasare sau de dublu schimb ) CuSO
4
+ 2NaOH Cu(OH)
2
+Na
2
SO
4

Cu(OH)
2
+ 4NH
4
OH [Cu(NH
4
)
4
](OH)
2

Formarea de compusi / Disocierea de compusi CaO + SiO
2
CaSiO
3

CaCO
3
CaO + CO
2

II. Reactii chimice cu modificarea starii sau numarului de oxidare (Reactiile de oxidare) vezi N.O. si valenta elementelor
care pot fi de mai multe tipuri:
Tablou general de prezentare




Tipuri de reactii redox
(i) reactii redox de combinare S + O
2
SO
2
(ii) reactii redox de deplasare (hidrogen, metal, halogeni )
deplasare poate fi realizata de un nemetal aspra altui nemetal
Cl
2
+ 2KBr 2KCl + Br
2
se explica prin caracterul nemetalic
Si + 2 H
2
O SiO
2
+ H
2
- se explica prin caldura de formare
deplasare poate fi realizata de un metal asupra altui metal sau hidrogenul din apa sau din acizi
Sr + 2H
2
O Sr(OH)
2
+ H
2


TiCl
4
+ 2Mg Ti + 2MgCl
2

Si atunci se explica pe baza seriei de activitate a metalelor




(iii) reactii redox de descompunere
2KClO
3
2KCl + 3O
2

(iv) reactii redox de disproportionare unul si acelasi element participa la oxidare si la reducere prin trecerea de la o stare de oxidare
la doua stari de oxidare inferiore si superiora celei iniziale:
Cl
2
+ 2OH
-
ClO
-
+ Cl
-
+ H
2
O

Cuplurile reactiilor redox

REDUCATORI
Cedeaza electroni se oxideaza
OXIDANTI
Acceptare de electroni se reduce
Hidrogenul, hidrurile Oxigenul, compusii bogati in oxigen
metalele Nemetalele puternic electronegative
Ionii metalici in stare de oxidare inferioara Oxoanionii nemetalici in stare inalta de oxidare
Oxizii metalelor in stare de oxidare inferioara Oxizii nemetalici in stare superiora de oxidare
Nemetalele slab electronegative
Oxizii nemetalici in stare de oxidare inferioara













Balansarea reactiilor redox in solutie medium de reactie

Balansarea reactiilor redox este strict condizionata de cunoasterea N.O.
Reguli de stabilire a numarului de oxidare si aplicatii
There are several rules for assigning the oxidation number to an element. Learning these rules will simplify the task of determining the
oxidation state of an element, and thus, whether it has undergone oxidation or reduction.
1. The oxidation number of an atom in the elemental state is zero.
Example: Cl
2
and Al both are 0
2. The oxidation number of a monatomic ion is equal to its charge.
Example: In the compound NaCl, the sodium has an oxidation number of 1+ and the chlorine is 1-.
3. The algebraic sum of the oxidation numbers in the formula of a compound is zero.
Example: the oxidation numbers in the NaCl above add up to 0
4. The oxidation number of hydrogen in a compound is 1+, except when hydrogen forms compounds called hydrides with active
metals, and then it is 1-.
Examples: H is 1+ in H
2
O, but 1- in NaH (sodium hydride).
5. The oxidation number of oxygen in a compound is 2-, except in peroxides when it is 1-, and when combined with fluorine.
Then it is 2+.
Example: In H
2
O the oxygen is 2-, in H
2
O
2
it is 1-.
6. The algebraic sum of the oxidation numbers in the formula for a polyatomic ion is equal to the charge on that ion.
Example: in the sulfate ion, SO
4
2-
, the oxidation numbers of the sulfur and the oxygens add up to 2-. The oxygens are 2-
each, and the sulfur is 6+.
Application Problems:
1. What is the oxidation number of chromium in Na
2
CrO
4
, Cr
2
O
7
2-
Exemplu: 2. Given the unbalanced equation below:
Cr
2
O
3(s)
+ Al
(s)
----> Cr
(s)
+ Al
2
O
3(s)

a. identify the oxidation state of each element
b. identify the oxidizing agent
c. identify the reducing agent


Pentru o reactie redox in solutie in care de exemplu are loc oxidarea unei ioduri in mediu acid de catre prmanganatul de potasiu

MnO
4
-
+ I
-
I
2
+ Mn
2+


se va tine cont atat de potentialul de oxidoreducere a fiecarui participant si de conditia ca forta electromotoare (FEM = E) sa fie mai
mare ca zero. Astfel pentru cazul in studiu numai pentru produsii de reactie I
2
si Mn
2+
,

FEM E
I-/I2
+ E
MnO4-/Mn2+

> 0
FEM = E pentru o reactie chimica a ox
1
+ b red
2
c ox
2
+ d red
1


E = E
0
(RT / nF ) ln K
unde:
E
0
= potentialul standard de oxidoreducere
R = 8.3145 J/K.mol
T = temperatura absoluta
n = numera de electroni transferati
F = 19500C sau 9.6485 x 10
4
J/V.mol

K = [ox
2]
c
[red
1 ]
d

/
[
ox
1
]
a
[ red
2]
b

Exemplu:
Fe(s) + Cd
2+
(aq) ------> Fe
2+
(aq) + Cd(s)

Fe
2+
(aq) + 2 e
-
------> Fe (s), E = -0.44 V
Cd
2+
(aq) +2 e
-
------> Cd (s), E = -0.40 V

FEM = + 0.44 0.40 = + 0.04 V
Atunci balansarea va avea in vedere atat produsii de reactie finali si numarul electronilor transferati cat si mediul de reactie care
asigura compensarea sarcinilor electrice in solutie si formeaza in pila electrica puntea de sare.
2 I
-
- 2e
-
I
2

MnO
4
-
+ 5 e
-
+ 8 H
+
Mn
2+
+ 4 H
2
O
Electronii transferati circula printr-un conductor si astfel reactiile redox devin sisteme pe baza carora se poate transforma energia
chimica in energie electrica;


Electroliza pila galvanica John Friederic Daniel
- consuma surent electric pentru desfacerea unui compus chimic - produce current electric pe baza unei reactii redox

Reactiile redox sursa de energie electrica
Bateria auto

Pb + PbO
2
+ H
2
SO
4
PbSO
4
+ H
2
O
Bateria uscata sau pila Leclanch

Zn(s) + 2 MnO
2
(s) + 2 NH
4
Cl(aq) ZnCl
2
+ Mn
2
O
3
(s) + 2 NH
3
(aq) + H
2
O









Tipuri de compusi chimici in chimia anorganica

H He
B C N O F Ne
Si P S Cl Ar
Ge As Se Br Kr
Sn Sb Te I Xe
Pb Bi Po At Rn

I. Combinatii binare ( formate din doua elemente )
1. hidrurile EH
n

2. halogenuri EX
n
(fluoruri, cloruri, bromuri, ioduri ) ionice NaCl, CaF
2,
AlBr
3,
covalente

SCl
2

3. oxizii E
2
O
n
(simpli, peroxizi, superoxizi, oxizi micsti de tip spinel )
4. E
2
S
n
sulfuri, seleniuri, telururi
5. E
3
N
n
azoturi, fosfuri, arseniuri
6. carburi, siliciuri

II. Combinatii ternare
1. hidroxizi E(OH)
n

2. oxoacizi H
n
EO
m
( orto, meta, piro)
III. Compusi donor acceptor
BF
3
+ NH
3
F
3
B NH
3


IV. Combinatii complexe

Calcule chimice - Probleme
1. gaze si conditiile normale
2. randament si puritate
3. reactii chimice in solutie (substanta in exces, concentratii )
4. solutii (F, T)

Starea naturala si raspandirea in natura a elementelor

Elementele chimice se gasesc in natura sub forma de minerale:
- mineralele contin elementele chimice in stare nativa ( elemente cu reactivitate scazuta se pot aproxima in jur de ~ 30
de elemente, de exemplu: C diamante, S, Au, Ag,.. si sub forma de compusi chimici.
- Mai multe minerale formeaza un minereu. Raspandirea elementelor chimice sub forma de minerale cuprinde


Minereurile Mineralele
Sunt provenite din: (i) native
(ii) compusi chimici
- separatiuni magmatice (magma infiltrate in roca) - oxizi, hidroxizi
- filoane (magma infiltrate in scoarta pamantului) - hidroxizi
- precipitari pe fundul apelor - azotati, fosfati
- sedimentare (dezagregari si spalari) - carbonati, silicati
- contact (magma intre doua roci diferite) - halogenuri
- sulfuri, sulfati




Abundenta elementelor chimice pe pamant si abundenta elementelor chimice in univers sunt doua aspecte diferite.
Geochimia stiinta fundamentata de Goldschdmidt 1920-1930 si se ocupa cu raspandirea elemntelor in natura (scoarta
Pamantului, hidrosfera si atmosfera ) si cu formarea mineralelor.


(i) Pamantul: miezul, invelisul miezului, manta, invelisul mantalei, scoarta pamantului;
(ii) Hidrosfera
(iii) Atmosfera ~57 km in jurul pamantlui



Cele mai raspandite elemente pe pamant sunt in general elementele cu numerele de ordine cele mai mici. In preocuparile
chimistului intra elementele aflate in litosfera, atmosfera, hidrosfera, in ordinal de marime a catorva zeci de km daca ar
fi sa comparam cu R
P
= 6371 km.
Litosfera - Pe baza unui numar mare de analize Clark 1924 stabileste compozitia elemntara a pamantului sub forma
procentelor de masa privind abundenta elementelor chimice.

Oxygen O2 Siliciu Si Aluminiu Al Fer Fe Calciu Ca Sodium Na

49% 26% 7.5% 4.7% 3.4% 2.6%


Potasiu K Magneziu Mg Hydrogen H
2
Titan Ti Clor Cl Fosfor P

24% 1.9% 0.9% 0.6% 0.2% 0.1%







In concluzie:
- unele elemente considerate comune Cu. Hg, Sn, As sunt in realitate foarte rare. Aparitia lor curenta este urmare a
faptului ca s-au concentrate in cantitati mari de minereuri localizate in putine regiuni de pe glob;
- alte elemente cum ar fi Ti, P, K desi mult mai raspandite in natura sunt foarte greu de obtinut tocmai din cauza
imprastierii uniforme.
- Multe elemente gazoase usoare ca He, Ne, H
2
, nu au fost retinute in campul gravitational al pamantului si au parasite
atmosfera pamantului.
- Multe elemente sunt considerate rare din cauza faptului ca se separa foarte greu de elementele cu care se aseaman a
chimic si cu care sunt amestecate cum ar fi: Be si Ga cu Al, Sr cu Ca, Hf cu Zr.
- Elementele cu numar atomic mai mare decat Ni sunt rare;
- Elementele cu numar atomic impar sunt mai rare decat cele cu numar atomic par.


Atmosfera inaltimea exacta a atmosferei nu poate fi marcata exact deoarece densitatea atmosferei scade progresiv cu altitudinea si nu se poate
delimita prcis atmosfera de spatiul interplanetary, dar se poate aprecia exact greutatea atmosferei de 1Kg/cm
2
ceea ce tine in echilibru o coloana
de mercur de 760 mm. Compozitia atmosferei este constanta pana la ~ 57 km. Atmosfera de deasupra scoartei terestre este formata din
urmatoarele straturi:

Ionosfera (200 Km - ) contine plasma diluata de ioni si electroni care se formeaza sub actiunea razelor X si a radiatiilor ultraviolete emise
de Soare. O mare parte din energia solara absorbita de moleculele gazelor din atmosfera produce o ionizare a acestora numita si fotoionizare
cand se produc in afara de electronii liberi si speciile ionice NO
+
, NO
2+
, O
2+
, O
+
, sporadic Na
+
, Mg
+
, Fe
+
, Si
+
, Ca
+
din meteoritii dezintegrati si
chiar H
3
O
+
, O
2+
, O
-
, O
2
-
, NO
3
-
, CO
3
2-
.
----------------------------------------------------------------------------------------------------------------------------------------------------------------------
Termosfera (130 200 Km)
----------------------------------------------------------------------------------------------------------------------------------------------------------------------
Mezosfera (60 130 Km) temperature scade si creste apoi din nou in regiunea periferica a termosferei. Noaptea are loc reactia de
recombinare si formare a ozonului cu eliberarea unei mari cantitati de caldura care asigura mentinerea temperaturii pe pamant.
O
2
+ h (1760A
0
)

2 O


O

+ O
2
O
3
+ Q 3 O

O
3
+ Q
-------------------------------------------------------------------------------------------------------------------------------------------------------------------
Stratosfera - (10-60 Km) temperatura creste cu inaltimea pana la 60 km, se afla ecranul de ozon care absoarbe radiatiile nocive sub 2900 A
0
O
3
+ h ( 2420A
0
) O

+ O
2
produsii de reactie adica radicalii de oxygen si moleculele de oxygen trec in mezosfera

-----------------------------------------------------------------------------------------------------------------------------------------------------------------------
Troposfera (0-10 Km) fenomenele meteorologice, Gazele care intra in componenta atmosferei sunt in principal (% de volum) 78% N
2
si 20% O
2
restul finnd completat in mod variabil de Ar, CO
2
, H
2
, He, Ne, Ar, Kr

Hidrosfera reprezinta 70.8% din suprafata pamantului.




Raspandirea elementelor in univers

Planete elemente observatii
H, He CO
2

Soare 15x10
6
K
0
.. x
Venus 425
0
C x p=100 atm
Marte ecuator +3
0
C si la poli -125
0
C ... x p=0.01 atm
Jupiter - 125
0
C x p = 1000 atm

Gazele interstelare din galaxia noastra contin 90% H atomic si 10% H
2
se afla intre planete pe distante de 20-30 ani lumina,
1 an lumina = 10
13
Km









NEMETALELE Starea naturala in care se gasesc elementele chimice clasificare dupa tipul de mineral

Tipul de mineral
DENUMIREA MINERALULUI SI STRUCTURA CRISTALINA






nativa
C
Diamantul grafit
S
Sulful nativ
Halogenuri



Fluoruri, Cloruri, bromuri



Halogenuri bazice, duble,
complexe







Fluorina CaF
2
Sarea gema NaCl Silvina KCl Bromargirit AgBr

atacamit CuCl(OH). Cu (OH)
2
Carnalita KClMgCl
2
6H
2
O Criolitul Na
3
[AlF
6
]



Sulfuri









galena PbS blenda ZnS pirita FeS
2
marcasita FeS
2










Sulfuri naturale ca pigmenti
















calcopirita CuFeS
2
stibina Sb
2
S
3

Cinabru HgS Realgarul As
4
S
4

Cristal roboedric.
- in froma granulara cristalizat trigonal .
-Duritate Mohs hardness 2-2.5 , lucios,
-greutate specifica 8.176,
-indice de refractie n = 2.905 n = 3.256 ,
-birefrigerenta = 0.351
-solubilitate 1.04 x 10
-25
g /100 ml apa (P ( 25C ) = 2 x 10
-32
)















SULFOARSENIURI







orpimentul As
2
S
3

Sistem monoclinic, duritate 1.5 2, greutate specifica 3.46. p.t. 300 C - 325 C. ind.refr. a=2.4, b=2.81,
g=3.02. (galben orange0

Nichelina NiS

cobaltite (Co,Fe)AsS arsenopirita FeAsS pirargirita Ag
3
SbS
3



OXIZI
X
2
O and XO





X
2
O
3




Fe



OXIZI SIMPLI

Cupritul Cu
2
O Zincitul ZnO Litarga PbO (rosu) forma dimorfa ortorombica PbO masicot
tetragonal crystal structure
duritate = 2, rosu .
Termenul de "litharge" poate fi combinat cu:
Hematitele



Fe
2
O
3
si

rosiatic

Pigmentii de pamant
Hematita, este mineralul format din oxidul feric (Fe
2
O
3
) cristalizat romboedric cu aceeasi structura cristalina ca
si corindonul. Hematite formeaza in continut de 20% - 70% pigmentii de tip ocru care se extrag din silicati prin
separarea nisipului la spalare, si apoi uscare. Cele mai bune Anglia, Mexic, Brazilia, Australia, USA Canada.


















Pigmentii pe baza de hematite
PIGMENTII OCRU
Rosu ocru, Fe
2
O
3
,
Ocru purpuriu Fe
2
O
3
, identic cu rosu dar particule de marime diferita in interactie cu lumina
Galben ocru Fe
2
O
3
H
2
O, cel mai bun in Franta, Roussilion
PIGMENTII UMBRA este un pigment de pamant brun, extras din Umbria o regiune muntoasa din Italia iar
cel mai bun din Cipru.
Culoarea devine intensa cand este calcinat si se numeste burnt umbra sau umbra arsa,
compozitia chimica
Fe
2
O
3
+ MnO
2
+ nH
2
O + Si + Al
2
O
3
Silicatii care contin hematite prin degradare dau un oxihidroxid goethita FeO(OH) , care da culoarea
rosie a solurilor tropicale. Are retea ortorombica. Poate fi considerate ca oxid de fier hidratat. Formeaza clasa
pigmentilor de pamant.

Goetita FeO(OH) PIGMENTUL SIENNA contine mineralul lepidocitul -FeO(OH
Limonitul este un amestec de oxid de fier (III) - ortorombic, duritate 5
si hidroxid FeO(OH)nH
2
O . este forma descompusa a
mineralelor de Fe



Al





Ti, Mn, Sn








SiO
2




Corindonul Al
2
O
3
este o roc ace contine mai multe minerale si poate avea impuritati de Fe, Ti, Cr. Prezinta specii
folosite ca pietre pretioase: rubinul specia rosie, safirul specia albastruie.
Grupa rutilului


Rutilul TiO
2
Structura tetragonala, unit cell parameters a=4.584, and c=2.953., densitate of 4240 kg/m
3
.
Pigment culoare alb stralucitor.
Pyrolusite MnO
2

Cassiterite SnO
2
SiO
2
dioxidul de siliciu sau silica este un oxid cu structura tetraedrica care manifesta proprietatea de
Oxizii micsti - spineli
polimorfism.

Cuart - rhombohedral (trigonal) 573
0
C Cuart - hexagonal -
Lanturi elicoidale optic active in lant difera unghiurile Si-O-Si de 155

Forme metastabile la presiune normala

-tridymite / orthorhombic -tridymite / hexagonal

1470 C

-cristobalite / tetragonal -cristobalite / cubic



Grupa ilmenitei impachetare cristalina asemanatoare cu corindonul
Ilmenite FeTiO
3

Spinel MgAl
2
O
4

Magnetite Fe
3
O
4
(Fe
2+
Fe
3+
2
O
4
)
Chromite FeCr
2
O
4




HIDROXIZI
Grupul Goetitei

Manganite MnO(OH)
Diaspore AlO(OH)


Saruri
oxigenate
Sulfati Sulfati anhidri : Barite BaSO
4,
Celestite SrSO
4,
Anglesite PbSO
4,
Anhydrite CaSO
4

Sulfatihidratati:Gypsum CaSO
4
2H
2
O,ChalcanthiteCuSO
4
5H
2
O,EpsomiteMgSO
4
7H
2
O,Melanterite FeSO
4
7H
2
O




Azotati

Salpetrul, salpetrul de Chile NaNO
3

Fosfati

Ca5(PO4)3(OH,F,Cl), Calcium (Fluoro, Chloro, Hydroxyl) Phosphate - apatite
Carbonate
Anhydrous carbonates
Calcite group: Trigonal - Calcite CaCO
3,
Gaspeite (Ni,Mg,Fe
2+
)CO
3,
Magnesite MgCO
3,
Otavite CdCO
3,
Rhodochrosite MnCO
3,
Siderite FeCO
3,
Smithsonite ZnCO
3,
Sphaerocobaltite CoCO
3

Aragonite group: Orthorhombic - Aragonite CaCO
3,
Cerussite PbCO
3,
Strontianite SrCO
3,
Witherite BaCO
3,
Natrite Na
2
CO
3

Dolomite group: Trigonal - Dolomite CaMg(CO
3
)
2

Carbonatii dubli Carbonate with hydroxide: Monoclinic Azurite Cu
3
(CO
3
)
2
(OH)
2,
Hydrocerussite
Pb
3
(CO
3
)
2
(OH)
2,
Malachite Cu
2
CO
3
(OH)
2,
Hydrozincite Zn
5
(CO
3
)
2
(OH)
6

Carbonate hidratati - Monohydrocalcite CaCO
3
.H
2
O, Natron Na
2
CO
3
10(H
2
O)
Silicate


SiO
2

Grupa quartului
Quartz - SiO
2,
Tridymite - SiO
2,
Cristobalite - SiO
2

[SiO
4
]
4
ORTOSILIOCATI




















borati
Phenacite group: Phenacite - Be
2
SiO
4,
Willemite - Zn
2
SiO
4,
Olivine group, Forsterite - Mg
2
SiO
4,
Zircon group : Zircon - ZrSiO
4

Topaz - Al
2
SiO
4
(F,OH)
2

(Si
x
O
3x
)
2x-
METASILICATI
-inele de 3-unitati (Si
3
O
9
)
6-
, 4-unitati (Si
4
O
12
)
8-
si 6-unitati (Si
6
O
18
)
12-

3-unitati: Benitoite - BaTi(Si
3
O
9
)
Si
2
O
5
PIROMETASILICATI.
Grupa argilelor: Kaolinite - Al
2
Si
2
O
5
(OH)
4,
Talc - Mg
3
Si
4
O
10
(OH)
2,
Mica group,
Lepidolite - K(Li,Al)
2-3
(AlSi
3
O
10
)(OH)
2

Glauconite - (K,Na)(Al,Mg,Fe)
2
(Si,Al)
4
O
10
(OH)
2

[SiO
4
]
4
[AlO
4
]
5
ALUMINOSILICATII DIN SCOARTA TERESTRA
Feldspar group,
Orthoclase- KAlSi
3
O
8,
Lazurite - (Na,Ca)
8
(AlSiO
4
)
6
(SO
4
,S,Cl)
2 -
feldspadoit
Natrolite - Na
2
Al
2
Si
3
O
10
2H
2
O grupa zeolitilor

Na
2
B
4
O
7
10H
2
O sau Na
2
[B
4
O
5
(OH)
4
]8H
2
O
Starea naturala Prezentare pe fiecare element chimic al tabelului periodic CONEXARE NEMETALE si METALE

H 1766 Cavendish
Cel mai abundent din
univers
He
B
- borati
C
- nativa
- carbonati


N
- nativa
- azotati
O
- nativa
- oxizi,
hidroxizi,
saruri
F
-fluoruri
Ne
Si
- oxid
- silicati

P
-fosfati
S
-sulfuri
-sulfati
Cl
-cloruri
Ar
Ge
- germaniuri


As
arseniuri
Se
-seleniuri
-sulfoseleniuri
Br
bromuri
Kr
Sn


Sb
- antimoniuri
Te
-telururi
I Xe
Pb Bi Po At Rn







Siateme cristaline retele cristaline impachetarea unitatii structurale intr-o retea Izomorfism, polimorfism
OXIZII E
2
O
n


Oxizii simpli
H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uuo
Uue Ubn
Alkali
metals
Alkaline earth metals Lanthanoids Actinoids Transition metals Other metals Metalloids Other nonmetals Halogens Noble gases



H
2
O He
Li
2
O BeO B
2
O
3
CO
2
N
2
O
5
O F
2
O Ne
Na
2
O MgO Al
2
O
3
SiO
2
P
2
O
5
SO
3
Cl
2
O
7
Ar
K
2
O CaO Sc
2
O
3
TiO
2
V
2
O
5
CrO
3
MnO
2
Fe
2
O
3
Co
2
O
3
Ni
2
O
3
Cu
2
O ZnO Ga
2
O
3
GeO
2
As
2
O
5
SeO
3
Br
2
O Kr
Rb
2
O SrO Y
2
O
3
ZrO
2
Nb
2
O
5
MoO
3
TcO
2
Ru
2
O
3
Rh
2
O
3
PdO Ag
2
O CdO In
2
O
3
Sn O
2
Sb
2
O
3
TeO
3
I
2
O
5
Xe
Cs
2
O BaO La
2
O
3
HfO
2
Ta
2
O
5
WO
3
ReO
2
Os
2
O
3
Ir
2
O
3
PtO Au
2
O HgO Tl
2
O
3
PbO
2
Bi
2
O
3
PoO At Rn
Fr
2
O RaO Ac
2
O
3
Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uuo
Uue Ubn

Ce
2
O
n
Pr
2
O
n
Nd
2
O
n
Pm
2
O
n
Sm
2
O
n
Eu
2
O
n
Gd
2
O
n
Tb
2
O
n
Dy
2
O
n
Ho
2
O
n
Er
2
O
n
Tm
2
O
n
Yb
2
O
n
Lu
2
O
n

Th
2
O
n
Pa
2
O
n
U
2
O
n
Np
2
O
n
Pu
2
O
n
Am
2
O
n
Cm
2
O
n
Bk
2
O
n
Cf
2
O
n
Es
2
O
n
Fm
2
O
n
Md
2
O
n
No
2
O
n
Lr
2
O
n


OXIZII SIMPLI AI NEMETALELOR

H
2
O +3 +2 +4 +1 +2 +3 +4 +5 +2 +4 +6 -1 +1 +4 +5 +6 +7

B
2
O
3
CO

CO
2
N
2
O

NO N
2
O
3
N
2
O
4
N
2
O
5

F
2
O


Al
2
O
3
SiO

SiO
2
P
2
O
3
P
2
O
5
SO
2
SO
3

Cl
2
O ClO
2
Cl
2
O
6
Cl
2
O
7


Ga
2
O
3
GeO GeO
2
As
2
O
3
As
2
O
5
SeO
2
SeO
3

Br
2
O BrO
2
BrO
3



In
2
O
3
Sn O Sn O
2
Sb
2
O
3
Sb
2
O
5
TeO

TeO
2
TeO
3

I
2
O
4
I
2
O
5
I
4
O
9


Tl
2
O
3
PbO

PbO
2
Bi
2
O
3
Bi
2
O
5
PoO PoO
2
PoO
3




SO
2
TeO
2
B
2
O
3
As
2
O
3
Sb
2
O
3



Obtinere

1. reactii de combinare sau sinteza direct din elemente element + oxygen oxid nemetalic

H
2
O +3 +2 +4 +1 +2 +3 +4 +5 +2 +4 +6 -1 +1 +4 +5 +6 +7
B
2
O
3
CO

CO
2



Al
2
O
3
P
2
O
3
P
2
O
5
SO
2

As
2
O
3
SeO
2

Sb
2
O
3


Bi
2
O
3






2. descompunerea acizilor oxigenati / a hidroxizilor hidroxid oxid metallic + apa
acid oxigenat oxid nemetallic + apa
H
2
O +3 +2 +4 +1 +2 +3 +4 +5 +2 +4 +6 -1 +1 +4 +5 +6 +7

B
2
O
3


CO
2


N
2
O
5




Al
2
O
3


SiO
2
P
2
O
3
P
2
O
5
SO
2
SO
3

Cl
2
O

Cl
2
O
7


GeO As
2
O
3
As
2
O
5

Br
2
O


Sn O Sb
2
O
3
TeO
3

I
2
O
5


Bi
2
O
3






3. descompunerea termica a sarurilor ( termica ) sare oxid metallic + oxid nemetalic
H
2
O +3 +2 +4 +1 +2 +3 +4 +5 +2 +4 +6 -1 +1 +4 +5 +6 +7



CO
2


N
2
O N
2
O
4

NH
4
NO
3
Pb(NO
3
)
2




SiO
2


SO
2
SO
2
GeO
2

Sn O






4. descompunerea sarurilor cu acizi ( saruri oxygenate de tip carbonate, sulfite, azotati, sulfati, azotiti)
5. prajirea sulfurilor / seleniuri / arseniuri ( sare + oxygen oxid metallic (metalloid) + oxid se sulf (selenium, arsen) )













6. metode speciale
IV
V VI VII
Inf sup
sup Inf sup Diferite situatii
CO


C + H
2
O

CH
4
+ H
2
O

HCOOH

CO
2


CO+O
2




P
2
O
5 /
As
2
O
5
As
2
O
3
/ P
2
O
3
+ oxid


F
2
O

F
2
+ NaOH



As
2
O
5


As
2
O
3
+HNO
3


As + HNO
3



SO
2

CaSO
4
+ C
H
2
SO
4
+ red


SO
3


SO
2
+ oxid
Cl
2
O

HgO + Cl
2


ClO
2


HClO
3


Cl
2
O
6

ClO
2
+ oxid





GeO

GeO
2 +
red

GeO
2

Ge + H
2
O
2


GeO + oxid



Sb
2
O
5

Sb + HNO
3






SeO
3



SeO
2
+ oxid
Br
2
O

HgO + Br
2



Sn O
SnO
2 +
red


Sn O
2
Sn + HNO
3




TeO
2
Te +HNO
3



PoO PoO
2
PoO
3


PROPRIETATI FIZICE Structura moleculara (legatuturi covalente), starea de agregare

E
2
O
IV V VI VII
- liniara
- angulara
N
2
O

N = N = O N
N O
:
..
- +
..
:
..
+
_

F
2
O Cl
2
O Br
2
O



Stare de
agregare/retea
cristalina
- gaz incolor, indoor, fara gust si
neinflamabil la temperature camerei

Utilizari/import
anta
- carburant pentru motoarele de racheta
ca adaos la carburanti pentru ca
permite o ardere completa a
combustibilului,
- adaos alimentar E 942 la vidarea
pachetelor alimentare.
- antianxios prin cresterea activitatii
receptorului GABA
A

F
2
O este un gaz periculos relative stabil deoarece poate fi amestecat
cu H2, CO, CH4 fara a reactiona dar la lovire exploadeaza violent
Cl
2
O gaz galben rosiatic care exploadeaza usor.
- inalbitor pentru lemn, faina,
- dezinfectant si in 1944 in America s-a folosit pentru indepartarea
fenolului din apa,
- in 1956 s-a utilizat ca inlocuitor al clorului care forma cu impuritatile
din apa halogenuri de metan.Este mai putin coroziv decat clorul,
- are effect dezinfectant asupra antraxului,
- prin stabilizarea solutiilor se poate folosi la tratamentele orale.
Br
2
O lichid brun roscat stabil numai la temperature joase.



EO
IV V VI VII
CO


C O :
: C=O : :C O :
- +
.. +
..
:
..
-

NO

N
O:
..
.
..



Gaz incolor, indoor, fara miros si fara gust,
foarte toxic, oxid inert.
Gaz incolor in stare solida este de
culoare albastra si se prezinta dimerizat


- folosit in sintezele organice,
- combinatii complexe tip carbonili
- NO este un produs de metabolism al
organismelor vii si un protector in
anumite cantitati al ficatului,









E
2
O
3

IV V VI VII
N
2
O
3



Structura propusa de microunde este cea de mai sus O = N N = O

O
Structura corespunzatoare anhidridei acide O = N O N = O este un isomer care nu a fost
observat. Este un lichid albastru stabil numai la temperature joase.



P
2
O
3
As
2
O
3
Sb
2
O
3



O
O
O
O
O
O



P
2
O
3
As
2
O
3
Sb
2
O
3

Solide incolore cu aspect sticlos sau de pudra. Oxidul fosforului a fost cel mai studiat. Oxidul arseniului
este una din cele mai vechi otravuri. Oxidul Sb prezinta termocromism la 570
0
C cand trece din alb in
galben. Toti oxizii prezinta in stare de vapori molecule P
4
O
6
As
4
O
6
Sb
4
O
6



Sb
4
O
6
- consumul anual in US si Europa este de aprox 10,000 and 25,000 t. principala aplicatie este ca
inhibitor al inflamabilitatii in combinatie cu halogenuri si se introduce in polimeri, textile, piele, carcase
de aparate. Agent de opacizare a sticlei, ceramicii, emailurilor, pigmenti, catalizator in obtinerea PET si
vulcanizarea cauciucului.





EO
2
/
E
2
O
4

IV V VI VII
CO
2


SiO
2


GeO
2

NO
2

N
O
O
.



N
2
O
4

SO
2


SeO
2





TeO
2

ClO
2


BrO
2

-cristale instabile
galben-orange
N N
O
O
O
O


- sursele de dioxid de azot sunt combustia
motoarelor si testele nucleare si cantitatea
trebuie monitorizata. In aer face un nor
rosiatic care a fost repartizat in 2009 in
troposfera in urmatoarele zone:
-
- gaz incolor cu miros
intepator,
- 2.2 ori mai greu decat aerul
- se lichefiaza usor la 25
0
C si
4atm,
-foarte bun solvent pentru
ceara, rasini si celuloza
acetate;
















E
2
O
5

IV V VI VII

N
2
O
5

- oxidul se poate prezenta si ca o sare solida continand cationul NO
2
+
si anionul
planar NO
3

. Solidul ar putea fi numit azotat de nitroniu, dar amandoua centrele


de azot au acelasi numar de oxidare +5.
- molecula cu structura O
2
N-O-NO
2
se obtine in faza gazoasa prin sublimarea sari
solide sau cand sarea solida se dizolva in solventi nepolari ca CCl
4
.
P
2
O
5
As
2
O
5
Sb
2
O
5

Pudra alba ca zapada solid amorf nu sublima - solid hidrofob
-
sublima P
4
O
10
- higroscopic

- afinitate pentru apa


I
2
O
5


- cel mai important oxid al iodului, solid
cristalizat, incolor, stabil pana la 300
0
C.
utilizari
P
4
O
10
- ca agent deshidratant pentru HNO
3
/ N
2
O
5
; H
2
SO
4
/ SO
3
; HClO
4
/ Cl
2
O
7
.
P
4
O
10
(am) + 6H
2
O (lq) 4H
3
PO
4
(c) (-177 kJ)
Dar are tendinta de a forma o pelicula viscoasa protectoare si de aceea se
foloseste sub forma granulara in exicator. Folosit in reactiile de obtinere ale
amidelor si nitrililor.
- solutiile de P
4
O
10
in DMSO, se folosesc la oxidarea alcoolilor.
As
2
O
5
Solid sau solutie se foloseste la obtinerea arseniatilor pentru adezivi metalici,
insecticide, fungicide, conservarea lemnului, cerneluri si coloranti.
Sb
2
O
5
- inhibitor de ardere

in ABS , plastics, flocculant in productiaof TiO
2

- productia sticlelor, pigmentilor si adezivilor.











IV V VI VII
EO
3
/E
2
O
6

SO
3

-in stare solida exista cel putin trei forme cristaline
aspect de gheta format din molecule ciclice (SO
3
)
3

, pt=68
aspect de azbest alb lucios din lanturi elicoidale pt
32.5
- lichid

SeO
3
TeO
3

ClO
3

Cl
2
O
3
, solid brun descoperit in 1967
exploziv chiar sun 0C.

da cu usurinta Cl
2
O
6
, cu structura
OCl-ClO
2
si cu un isomer posibil
Cl-O-ClO
2
.




IV V VI VII
E
2
O
7

Cl
2
O
7



Cl
2
O
7
molecula endoterma, instabila, 2 Cl
2
O
7
2 Cl
2
+ 7 O
2
(H = 135 kJ/mol)
In acest compus clorul exista in cea mai inalta stare de oxidare +7, desi legaturile
sunt de tip covalent. Lichid uleios si incolor.


PROPRIETATI CHIMICE oxizii nemetalelor prezinta urmatoarele proprietati chimice

+2 +4 +1 +2 +3 +4 +5 +2 +4 +6 -1 +1 +4 +5 +6 +7
CO

CO
2
N
2
O

NO N
2
O
3
NO
2
/N
2
O
4
N
2
O
5

F
2
O

SiO

SiO
2
P
2
O
3
P
2
O
5
SO
2
SO
3

Cl
2
O ClO
2
Cl
2
O
6
Cl
2
O
7

GeO GeO
2
As
2
O
3
As
2
O
5
SeO
2
SeO
3

Br
2
O BrO
2
BrO
3


Sn O Sn O
2
Sb
2
O
3
Sb
2
O
5
TeO

TeO
2
TeO
3

I
2
O
4
I
2
O
5
I
4
O
9

PbO

PbO
2
Bi
2
O
3
Bi
2
O
5
PoO PoO
2
PoO
3




Tipuri de reactii chimice Reactii Observatii
1. oxid nemetalic + apa acid
oxigenat

CO
2
N
2
O
3
NO
2
/N
2
O
4
N
2
O
5
P
2
O
3
P
2
O
5
SO
2
SO
3
Cl
2
O ClO
2
Cl
2
O
6
Cl
2
O
7
Br
2
O

2. oxid nemetalic + oxid metalic
sare

Atentie pentru oxizii care dau anhydride mixte
3. oxid nemetalic + hidroxid sare +
apa

Atentie pentru oxizii care dau anhydride mixte
4. oxid nemetalic + acid sare + apa


5. oxid nemetalic + in reactii redox

F
2
O - metalele da oxizi si fluoruri
- nemetalele P/ PF
5
and POF
3
; S / SO
2
and SF
4
; Xe / XeF
4
and
xenon oxyfluorides.
- Compusi
OF
2
(aq) + H
2
O (aq) 2 HF (aq) + O
2
(g)
OF
2
+ SO
2
SO
3
+ F
2
OF
2
+ 2SO
2
+ UV radiation S
2
O
5
F
2
pyrosulfuryl fluoride,
S
2
O
5
F
2
:

1+
Cl
2
O HgO + 2 Cl
2
Cl
2
O + HgCl
2
.HgO

4+
ClO
2
(i) NaClO
3
+ H
2
SO
4
+ SO
2
ClO
2
+ NaHSO
4

(ii) KClO
3
+ H
2
SO
4
HClO
3
+ NaHSO
4

HClO
3
ClO
2 +
HClO
4
+ H
2
O
(iii) AgClO
3
+ Cl
2
AgCl + ClO
2
+ O
2

(iv) NaClO
2
+ Cl
2
ClO
2
+ NaCl
- tendinta mai mica de dimerizare pentru ca e neimperecheat nu este localizer pe atomul
central
- este anhidrida mixta 2 ClO
2
+ H
2
O HClO
2
+ HClO
3

-

2 ClO
2
+ 2 NaOH NaClO
2
+ NaClO
3
+ H
2
O
- Este un oxidant puternic (P
4
in laborator, si H
2
O
2
)
- 2 ClO
2
+ 2 NaOH + H
2
O
2
NaClO
2
+ O
2
+ H
2
O
- Inalbitor pentru textile, hartie, faina, nu este periculos in amestec cu aerul


6+
ClO
3
/ Cl
2
O
6
monomerul este foarte instabil si trece in dimmer care se poate obtine si prin oxidare
ClO
2
+ O
3
Cl
2
O
6
+ 1/2O
2
-
este anhidrida mixta Cl
2
O
6
+ H
2
O HClO
3
+ HClO
4

Cl
2
O
6
+ 2 NaOH NaClO
3
+ NaClO
4
+ H
2
O
7+
Cl
2
O
7
nu se remarca in mod deosebit


Br
2
O lichid rosu-brun, se obtine in acelasi mod cu omologul sau Cl
2
O

5+
I
2
O
5
anhidrida acidului iodic I
2
O
5
+ H
2
O HIO
3

- importanta pentru dozarea CO cu care reactioneaza cantitativ:
- I
2
O
5
+ 5CO I
2
+

5CO
2

7+
(I
2
O
7
) polimer solid de culoare orange

I
2
O
4
IO (IO
3
) iodat de iodosil

I
4
O
9
I(IO
3
)
3
iodat de iod

SO
2
-
arderea sulfului in aer imbogatit cu oxygen, apar si cantitati mici de SO
3

- arderea FeS2, ZnS, PbS, metoda industriala,
-
incalzirea sulfitilor cu H
2
SO
4
- reducerea CaSO
4
+ C
- reducerea H
2
SO
4
cu metale si nemetale Cu, S, C, NaBr,
-in urme de apa se transforma in H
2
SO
3
,
-se oxideaza usor la SO
3

Reducator cu (HNO
3
, NO, BaO
2
, Cl
2
)
-se reduce la S cu (H
2
, CO, C, CaS la T>100 CaO + S,T<100 CaSO
4
+ S
-in stare lichida se obtin oxoclorurile metalice si nemetalice
MoCl
5
+ SO
2
MoOCl
3
+ SOCl
2
PCl
5
+ SO
2
POCl
3
+ SOCl
2
Poluant foarte nociv al aerului ex intr-o zi de iarna la NY se emana ~2000t SO
2




SO
3
- este foarte reactive, cu apa da acidul sulfuric fiind anhidrida acestui acid, se foloseste la sulfonari in
chimia organica.

N
2
O
x
N
2
O se obtine din descompunerea azotatului de amoniu si este putin reactiv
NO

- se obtine prin reactia

HNO
3
cu metale mai putin active, NH
3
la oxidare cu O
2
(Pt)
- se oxideaza rapid la oxizi superiori (O2, X2, KMnO4)
- se reduce cu SO
2

- Se comporta atipic pentru o molecula paramagnetica, nu se dimerizeaza ci se asociaza si
atinge starea de diamagnetism
N
2
O
3
- este prima forma de oxidare cu O2 a NO,
- HNO3 prin reducere cu As2O3 da acest oxid
- La temperature scazuta este un lichid albastru pal
N
2
O
4
se formeaza prin dimerizarea NO
2
oxidului paramagnetic brun
- se mai obtine din actiunea acidului sulfuric asupra NaNO2,
- descompunerea Pb(NO
3
)
2
PbO + NO
2
+ O
2

- este anhidrida mixta N
2
O
4
+ H
2
O HNO
2
+ HNO
3

- N
2
O
4
+ 2CaO Ca(NO
2
)
2
+ Ca(NO
3
)
2

- Oxidant cu H2S trece la NO
- Se descompune diferit in faza gazoasa in doi radicali
- N
2
O
4



.
NO +
.
NO
3
iar in faza lichida in
N
2
O
4


NO
+
+ NO
3

N
2
O
5
anhidrida acidului azotic are o comportare asemanatoare in faza gazoasa si in lichid
N
2
O
5



.
NO
2
+
.
NO
3
iar in faza lichida in
N
2
O
5


NO
2
+
+ NO
3



P
4
O
6
, - P
4
in aer
- PCl
3
+ HCOONa P
2
O
3
+ NaCl + CO + H
2
O
- Instabil in aer, theoretic anhidrida H
3
PO
3

- P
2
O
3
+ HCl PCl
3
+ H
3
PO
3


P
4
O
10
- anhidrida acidului H
3
PO
4
- se poate reduce cu C la P
4
si CO
- P
2
O
3
+ HCl PCl3 + H3PO3
- P
2
O
3
+ HCl POCl
3
+ HPO
3
+ H
2
O

CO se obtine prin arderea incomplete a C, deshidratarea HCOOH, C, CH
4
+ vapori de apa, are
proprietati de ligand si formeaza clasa carbonililor.

CO
2
importanta pentru viata si circuitul in natura.

SiO
2







SiO
2
- reactioneaza cu
SiO
2
F
2
SiF
4

+
O
2
C metale
Si
+
CO (M
2
On)
HF
SiF
4
, H
2
[SiF
6
}
NaF SiF
4

+
Na
2
O
MgO
Mg
2
SiO
4
topire
+
SiO
2
= MgSiO
3
NaOH
Na
4
SiO
4
CaSO
4
CaSiO
3

+
SO
2

+
O
2
C
3
(PO
4
)
2
CaSiO
3

+
CO
+
P
4
CaCO
3
,
Na
2
CO
3
sticla
(Pyrex, Jena, Bohemia)
gel si fume silica



UTILIZARI si IMPORTANTA
1
HIDROXIZII M(OH)
n

..
-
:O-H
..



Hidroxizii sunt compusii anorganici care contin grupa functionala hidroxil OH

legata ionic de un ion metalic M
n+
cu formula generala
M(OH)
n
Acesti compusi anorganici nu trebuie confundati cu compusii organici hidroxilici ( alcooli si fenoli ) in care gruparea OH este legata covalent de
un rest hidrocarbonat. CH
3
OH), it is known as a hydroxyl group.
LiOH Be(OH)
2
B
2
O
3
CO2 N
2
O
5
O F
2
O
Na OH Mg(OH)
2
Al(OH)
3
SiO2
P
2
O
5
SO
3
Cl
2
O
7

K OH Ca(OH)
2
Sc(OH)
3
Ti(OH)
4
V
2
O
5
Cr(OH)
3
Mn(OH)
2
Fe(OH)
3
Co(OH)
3
Ni(OH)
2
Cu(OH)
2
Zn(OH)
2
Ga (OH)
3
Ge(OH)2 As
2
O
5
SeO
3
Br
2
O
Rb OH Sr(OH)
2
Y(OH)3 Zr(OH)4 Nb
2
O
5
MoO
3
TcO
2
Ru
2
O
3
Rh
2
O
3
PdO Ag
2
O CdO In(OH)
3
Sn (OH)2 Sb(OH)3 TeO
3
I
2
O
5

Cs OH Ba(OH)
2
La(OH)3 Hf(OH)4 Ta
2
O
5
WO
3
ReO
2
Os
2
O
3
Ir
2
O
3
PtO Au
2
O HgO Tl (OH)
3
Pb(OH)2
Bi(OH)3 PoO At
Fr OH Ra(OH)
2
Ac
2
O
3
Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus
Ce
2
O
n
Pr
2
O
n
Nd
2
O
n
Pm
2
O
n
Sm
2
O
n
Eu
2
O
n
Gd
2
O
n
Tb
2
O
n
Dy
2
O
n
Ho
2
O
n
Er
2
O
n
Tm
2
O
n
Yb
2
O
n
Lu
2
O
n

Th
2
O
n
Pa
2
O
n
U
2
O
n
Np
2n
Pu
2
O
n
Am
2
O
n
Cm
2
O
n
Bk
2
O
n
Cf
2
O
n
Es
2
O
n
Fm
2
O
n
Md
2
O
n
No
2
O
n
Lr
2
O
n


2

1. Clasificarea hidroxizilor
In functie de numarul grupelor hidroxil
- Monoacizi MOH: NaOH, KOH, NH
4
OH
- Diacizi M(OH)
2
: Ca(OH)
2
, Mg(OH)
2
, Ba(OH)
2
, Zn(OH)
2
, Cu(OH)
2
, Cd(OH)
2
, Pb(OH)
2
, Sn(OH)
2,
Fe(OH)
2

- Poliacizi M(OH)
3
: Al(OH)
3
Fe(OH)
3
Cr(OH)
3
Co(OH)
3

- M(OH)
4
: Ti(OH)
4,
Zr(OH)
4

In functie de taria bazica comportarea in solutii apoase
- hidrozi tari/ baze tari: NaOH, KOH, Ca(OH)
2
, Mg(OH)
2
, Ba(OH)
2

- hidroxizi slai / baze slabe: NH
4
OH, Zn(OH)
2
, Cu(OH)
2
, Cd(OH)
2
, Pb(OH)
2
, Sn(OH)
2,
Fe(OH)
2

In functie de solubilitate
- solubili: NaOH, KOH, Ca(OH)
2
, Mg(OH)
2
, Ba(OH)
2
, NH
4
OH
- insolubili: Al(OH)
3
Fe(OH)
3,
Fe(OH)
2

2. Metode de obtinere
Metal + apa
Oxid bazic + apa
sare + hidroxid
3. proprietatile fizice
- solide cristaline, incolore sau colorate in functie de natura ionului metallic care poate sa produca deformarea anionului hidroxil
4. proprietatile chimice
3
hidroxid + acid
hidroxid + oxid acid
hidroxid + sare
hidroxid + metal



1
ACIZII H
n


Acizii sunt compusii anorganici care contin un radical anorganic A legat printr-o covalenta polara de atomi de hydrogen ionizabili. In functie de
natura radicalului A acizii se clasifica in:
1. Hidracizi radicalul acid este un anion nemetalic X
-
= F
-
, Cl
-
, Br
-
, I
-
, S
2-
, H
n
A
2. Oxoacizi radicalul acid este un radical oxigenat. Pentru a intelege provenienta acestui radical oxigenat se considera theoretic ca intr-o
perioada fiecare element poate grupa in jurul sau un numar de grupe OH egal cu numarul grupei dar se stabilizeaza prin pierderea apei.
Formula generala a uni acid oxigenat este (HO)
n
(XO
p
)
m
:

I II III IV V VI VII
Per 3
NaOH Mg(OH)
2
Al(OH)
3
Si(OH)
4
P(OH)
5
S(OH)
6
Cl(OH)
7



Na
+
OH
-


Mg
2+
2 OH
-



Al
3+
3OH
-

Si
OH
OH
OH
HO

P
OH
OH
OH
HO
HO

S
OH
OH
OH
OH
HO
HO

Cl
OH
OH
OH
OH
OH
HO
HO

- H
2
O - 2 H
2
O - 3 H
2
O

P OH
OH
HO
O

OH HO
O
O
S

Cl
OH
O
O
O

2
1. Hidrurile cu character acid numite hidracizi sunt cele ale elementelor nemetalice din grupa VI/16 si VII/17





3. OXOACIZII
IV V VI VII
4+ 3+ 5+ 4+ 6+ 1+ 3+ 5+ 7+
2 H
2
CO
3
HNO
2
HNO
3

3 H
4
SiO
4
H
3
PO
3
H
3
PO
4
H
2
SO
3
H
2
SO
4
HClO HClO
2
HClO
3
HClO
4

4 H
3
AsO
3
H
3
AsO
4
H
2
SeO
3
H
2
SeO
4
HBrO HBrO
2
HBrO
3

5 H
2
TeO
3
H
2
TeO
4
HIO HIO
3
HIO
4







VI VII
HF Acid fluorhidric
H
2
S Acid sulfhidric hydrogen sulfurat HCl Acid clorhidric
H
2
Se Acid selenhidric HBr Acid bromhidric
H
2
Te Acid telurhidric HI Acid iodhidric
3
- tabelul de clasificare si Nomenclatura
Acid al Acid.hidric Acid hipoos Acid os

Acid.ic Acid peric orto Meta/os, ic Piro/os, ic Poli/os, ic
F HF
Cl HCl HClO HClO
2
HClO
3
HClO
4

Br HBr HBrO HBrO
2
HBrO
3

I HI HIO HIO
3
HIO
4
H
7
IO
7

CN HCN
S H
2
S H
2
SO
3
H
2
SO
4
H
2
S
2
O
7
HO
3
S-SO
3
H
N H
3
N
P H
3
PO
2
H
3
PO
3
H
3
PO
4
H
3
PO
4
HPO
3
H
4
P
2
O
7
polifosforici
As H
3
AsO
2
H
3
AsO
3
H
3
AsO
4
H
3
AsO
4
HAsO
3
H
4
As
2
O
7

Sb H
3
SbO
2
H
3
SbO
3
H
3
SbO
4
H
3
SbO
4
HSbO
3

C H
2
CO
3

Si H
4
SiO
4
H
2
SiO
3

Sn H
2
SnO
3

B H
3
BO
3

Cr H
2
CrO
4
H
2
Cr
2
O
7

H
2
MnO
4
HMnO
4

saruri .ura hipoit ..it .at perate


4
1. Clasificarea oxoacizi
- in functie de caracterul acido basic
- acizi monobazici: HCl, HF, HBr, HI, HNO
3,
HClO, HClO
2
HClO
3,
HClO
4,
- un proton ionizabil
- acizi dibazici: H
2
CO
3,
H
2
SO
3
, H
2
SO
4,
- doi protoni ionizabili
- acizi polibazici: H
3
PO
3,
H
3
PO
4,
H
3
AsO
4
, H
4
SiO
4
trei sau mai multi protoni ionizabili
- in functie de comportarea in solutii apoase
- acizi tari: sunt total ionizati in solutii apoase ( apreciere relativa deoarece comportamentul se poate modifica in alte tipuri de solventi; HCl,
HBr, HI, HNO
3,
HClO
4,
H
2
CO
3,
H
2
SO
4,

- acizi slabi: sunt slab disociati in solutii apoase: HClO, H
2
SO
3,
H
2
CO
3,
HF

2. Metode de obtinere
- combinarea directa intre hidrogen si nemetale ( hidracizi) HF HCl HBr HI H
2
S H
2
Se H
2
Te
fluorul reactioneaza violent cu hidrogenul si dezvolta o flama cu o temperature de 4000-5000
0
C
clorul bromul si iodul reactioneaza in conditii diferite si cu o reactivitate mult mai scazuta decat fluorul,
- actiunea oxizilor nemetalici cu apa (oxoacizi)
- actiunea unui acid nevolatil cu o sare a unui acid volatil (hidracizi si oxoacizi) HF, HCl, H
2
S,
- metode hidrolitice PCl
3
, PCl
5
, PBr
3
, PBr
5
, PI
3,
CaS, BaS, SrS, Al2S3
- halogenarile din chimia organica
- metode specifice: H
2
S ( C + H
2
O + S); ( CO + H
2
O + S); ( CH
4
+ S)
Proprietatile fizice, chimice si structura acizilor va fi dezvoltata in capitolul saruri, pentru ca unii dintre acizi sunt importanti prin
sarurile lor.
SARURILE

Sarurile sunt compusi care contin un ion pozitiv altul decat hidroniu si un ion negative altul decat hidroxilul. Cationul este de obicei un cation
metallic sau un cation complex iar anionul este un radical al uni acid. Astfel sunt sarurile provenite de la:
- hidracizi ( floruri, cloruri, bromuri, ioduri, sulfuri, seleniuri etc..)
- oxoacizi ( carbonati, silicati, azotiti, azotati, fosfiti, fosfati, arseniti, arseniati, sulfite, sulfati, seleniti, seleniati )

Clasificare
-
saruri normale: NaCl, K
2
SO
4
, NH
4
NO
3
- saruri acide: NaHCO
3
, KHSO
4
, CaHPO
4

- saruri bazice: CuCO
3
.Cu(OH)
2
, PbCO
3
, Pb(OH)
2

-
saruri duble: alaunii KAl(SO4)
2
, Ca(OCl)
2
.CaCl
2
, K
2
CO
3
.Na
2
CO
3
- saruri complexe: K
4
[Fe(CN)
6
], [Cu(NH
3
)
4
]SO
4


Metode de obtinere
- fara modificarea starii de oxidare
1. oxid nemetalic + oxid metallic
2. oxid nemetalic + baza
3. oxid metalic + acid
4. acid + baza
5. acid + sare
6. baza + sare
- cu modificarea starii de oxidare
1. metal + acid
2. metal + baza
3. nemetal + sare
4. metal + baza
5. nemetal + baza
6. descompunerea termica
Proprietati
A. sarurile difera prin solubilitate
Clasificarea scurta a sarurilor insolubile/solubile

Soluble Insoluble
Group I and NH
4
+
compounds Carbonates (Except Group I, NH
4
+
and uranyl compounds)
Nitrates Sulfites (Except Group I and NH
4
+
compounds)
Acetates (Ethanoates) (Except Ag
+
compounds) Phosphates (Except Group I and NH
4
+
compounds)
Chlorides, bromides and iodides (Except Ag
+
, Pb
2+
, Cu
+
and Hg
2
2+
) Hydroxides and oxides (Except Group I, NH
4
+
, Ba
2+
, Sr
2+
and Tl
+
)
Sulfates (Except Ag
+
, Pb
2+
, Ba
2+
, Sr
2+
and Ca
2+
) Sulfides (Except Group I, Group II and NH
4
+
compounds)

Reactia cu alte saruri, baze sau acizi
Hidroliza
Sarurile hidratate








Radicalul acid
Saruri .uraaosa/ica hipoit.os/ic ..it.os/ic .at..os/ic perate.os/ic
orto Meta os, ic Piro os, ic Poli os, ic
F F
-

Cl Cl
-
ClO
-
ClO2
-
ClO3
-
ClO4
-

Br Br
-
BrO
-
BrO2
-
BrO3
-

I I
-
IO
-
IO3
-
IO4
-
IO7
-

CN CN
-

S S
2-
SO3
2-
SO4
2-
S2O7
2-

-
O3S-SO3
-

N N
3-
NO2
-
NO3
-

P H2PO2
-
PO3
3-
PO4
3-
PO4
3-
PO3
-
P2O7
4-
polifosforici
As H2AsO2
-
AsO3
3-
AsO4
3-
AsO4
3-
AsO3
-
As2O7
4-

Sb H2SbO2
-
SbO3
3-
SbO4
3-
SbO4
3-
SbO3
-

C CO3
2-

Si SiO4
4-
SiO3
2-

Sn SnO3
2-

B BO3
3-

Cr CrO4
2-
Cr2O7
2-

Mo MoO4
2-

W MoO4
2-

Mn MnO4
2-
MnO4
-

metal
- cationii (Li
+
, Na
+
, K
+
, Cs
+
, Rb
+
si NH
4
+
dau in general saruri solubile cu exceptia acidului hexafluoro silicic H
2
[SiF
6
]
- NO
3
-
sunt solubili
- Cl
-
, Br
-
, I
-
insolubili AgCl, PbBr
2
, Hg
2
Cl
2
. F
-
insolubile CaF
2
BaF
2
, MgF
2,
PbF
2

- Ag
+
singurele solubile AgNO
3
acetatul de AgOOCCH
3

- SO
4

2-
insolubili BaSO
4
, PbSO
4
, Ag
2
SO
4
, SrSO
4
.
- OH
-
insolubili Fe(OH)
3
, Al(OH)
3
, Co(OH)
2
; Fe(OH)
2,
Cu(OH)
2,
Ni(OH)
2,
Zn(OH)
2

- S
2-
insolubili CdS, FeS, ZnS, Ag
2
S As
2
S
3
, Sb
2
S
3
, Bi
2
S
3
.
- CO
3

2-
insolubili Ca CO
3
, Sr CO
3
, Ba CO
3
, FeCO
3
, PbCO
3
.
- CrO
4
2-
insolubili PbCrO
4
, BaCrO
4




IV V VI VII
4+ 3+ 5+ 4+ 6+ 1+ 3+ 5+ 7+
2 H
2
CO
3
HNO
2
HNO
3

3 H
2
SiO
4
H
3
PO
3
H
3
PO
4
H
2
SO
3
H
2
SO
4
HClO HClO
2
HClO
3
HClO
4

4 H
3
AsO
3
H
3
AsO
4
H
2
SeO
3
H
2
SeO
4
HBrO HBrO
2
HBrO
3

5 H
2
TeO
3
H
2
TeO
4
HIO HIO
3
HIO
4



Carbonatii si bicarbonatii






Carbonatii naturali
Carbonati anhidri system Trigonal - grupa calcitei si carbonatii dubli de tip dolomite CaCO
3
Calcite
,

(Ni,Mg,Fe
2+
)CO
3
Gaspeite

MgCO
3
Magnesite
,
FeCO
3
Siderite , ZnCO
3,
Smithsonite, CaMg(CO
3
)
2
Dolomite
Carbonati anhidri system ortorombic - grupa aragonitei CaCO
3
Aragonite
PbCO
3
ceruzita
,
SrCO
3
Strontianita
,
BaCO
3
witerita
,
Na
2
CO
3
sodalita

Carbonati anhidri system monoclinic
2Cu (CO
3
)
2
Cu (OH)
2
Azurite
,
Cu (CO
3
)
2
Cu (OH)
2
Malachite
,
2Pb(CO
3
) Pb (OH)
2
Hidroceruzita
,
2 Zn CO
3
.

3 Zn(OH)
2
Hidrozincite

Carbonati hidratati -
CaCO
3
.6(H
2
O), MgCO
3
5(H
2
O), CaCO
3
.H
2
O, monohidrocalcita, Na
2
CO
3
10(H
2
O) natronul




Carbonati de sinteza
Na
2
CO
3
/ NaHCO
3

Leblanc process - In 1791, the French chemist Nicolas Leblanc patented a process for producing sodium carbonate from salt, sulfuric acid,
limestone, and coal. First, sea salt (sodium chloride) was boiled in sulfuric acid to yield sodium sulfate and hydrogen chloride gas, according to
the chemical equation

2 NaCl + H
2
SO
4
Na
2
SO
4
+ 2 HCl
Na
2
SO
4
+ CaCO
3
+ 2 C Na
2
CO
3
+ 2 CO
2
+ CaS
The sodium carbonate was extracted from the ashes with water, and then collected by allowing the water to evaporate. The hydrochloric acid
produced by the Leblanc process was a major source of air pollution, and the calcium sulfide byproduct also presented waste disposal issues.
However, it remained the major production method for sodium carbonate until the late 1880s.
[12][13]

Solvay process -- Solvay process - In 1861, the Belgian industrial chemist Ernest Solvay developed a method to convert sodium chloride to
sodium carbonate using ammonia. The Solvay process centered around a large hollow tower. At the bottom, calcium carbonate (limestone) was
heated to release carbon dioxide:
CaCO
3
CaO + CO
2

NaCl + NH
3
+ CO
2
+ H
2
O NaHCO
3
+ NH
4
Cl
2 NaHCO
3
Na
2
CO
3
+ H
2
O + CO
2

CaO + H
2
O Ca(OH)
2

Ca(OH)
2
+ 2 NH
4
Cl CaCl
2
+ 2 NH
3
+ 2 H
2
O
By 1900, 90% of sodium carbonate was produced by the Solvay process, and the last Leblanc process plant closed in the early 1920s.


CaCO3
Materia prima pentru tehnica fresco: Ca(OH)
2
, nisip, silicati colorati, pe care se aplica direct pigmentul. La prelucrare pasta de var ( terci de
Ca(OH)
2
si apa ) reactioneaza cu CO2, din aer si devinein parte carbonat de calciu CaCO
3
, insolubil care actioneaza ca un liant pentru pigment,
fapt care face fresca durabila dar in acelasi timp vulnerabila la conditiile de mediu.

Etape de preparare a unei fresce

1. calcinarea CaCO3 la at 800-900
0
C CaCO3(s) CaO(s) + CO2(g) (1)
2. obtinerea varului stins cand se adauga 2-3 moli apa la un mol de CaO se obtine pasta de var ca un gel foarte fin de Ca(OH)2

CaO(s) + H2O(l) Ca(OH)2(s) + caldura (2)

Istoric acest process se realizeaza in gropi in timp de 6 luni pentru a obtine o anume consistenta a pastei. In timpul lui Michelangelo acest
process dura si pana la 10 ani cand avea loc si o anume imbatranite a pastei de var. pasta de var este apoi amestecat in anumite proportii cu nisip
sau praf de marmura. Peretele era apoi acoperit cu mai multe starturi de fresca in care se descrestea progresiv proportia si marimea particulelor
de nisip.
- Primul strat arricio de 1-2 cm grosime contine 1 parte de pasta de var / 2 parti de nisip ( unele tehnici folosesc mai multe starturi de arricio. In
momentul in care arricio se intareste pe perete au loc mai multe procese fizice si chimice: - se absoarbe apa in perete, se evapora papa de
suprafata, se carbonateaza o parte din hidroxidul de calciu din pasta Ca(OH)
2
(s) + CO
2
(g) CaCO
3
(s) + H
2
O(l) (3). In timpul uscarii
startului de arricio artistul deseneaza mai intai cu carbune si apoi cu un pigment amestecat in apa si compatibil cu varul si apoi se imprima pe
hartie desenul pentru a servi drept ghid. Ultimul strat este intonaco 0.1-1 cm grosime cu un continut mai mic de nisip decat arricio. De obicei
intonaco se aplica pe portiuni mici peste care se si picteaza imediat giornata. Hartia cu sinopia este pusa peste intonaco proaspat si imaginea se
transfer ape parcursul a doua zile. Pigmentul se amesteca cu apa si se pensuleaza umed pe intonaco si se fixeaza odata cu carbonatarea
mortarului. In timp ce un mortar umed produce nuante vii un mortar uscat produce nuante pale si integrarea unui pigment in mortar uscat este de
neiertat.
Sand
Sand makes plaster porous and thus facilitates the transformation of caustic lime into carbonate of lime. The texture of sand is important.
Coarser sand is best for the undercoat and fine sand for the upper coats of plaster (there will be specific grain sizes suggested later.) All the sand
should be of a uniform grit and the grains should be angular in shape. They should feel sharp and not roll like a ball between the finger. The idea
is to squeeze the mortar tight.
An artist must be particular about the type of sand mixed into the lime plaster. And once the proper sand is chosen, the sand must be washed and
stored off the ground.
Sand must be free of loam, clay, mica, and gypsum. Humus and loam in sand are dangerous because they decompose when exposed to air and
cause efflorescence. Clay mixed in with the sand causes cracks in mortar. Water soaked sand containing clay weeps, exudes moisture, and makes
it difficult for colors to adhere. Sand containing mica flakes will eventually split off from the surface of the fresco. Never use sand containing
cement or gypsum because of efflorescence and decay.
The safest sand comes from solid rock - gneiss, granite or porphyry. Ground pumice and unglazed triturated porcelain work well. Sand made
from marble is also good and most desirable in certain instances. The decision to use sand or marble is personal. Sand gives the wall a warm
tone and marble dust or meal makes the background wall whiter.
Sand washing is easily done with: two wooden horses, two screens of different mesh, the first of 28-34 mesh with metal lath underneath, the
second of 16/square inch, water hose, grooved drying platform.

Sift the sand through the larger screen rinsing it well with water. Dry the sorted sand sizes separately. When dry store in separate bags. The final
sifting is done directly into the mortar box. Marble meal and dust is washed just like the sand. The coarser sand is used in the first two coats of
lime-plaster; the finer sand is used in the 3rd coat and the final coat or intonaco





Deteriorarea picturilor pe fresca depinde de porozitatea mortarului, aderenta lui pe perete, locuri unde apoi se vor forma sarurile
solubile. Aceste saruri vor acoperi picture si prin recristalizari successive vor produce dislocarea pigmentului de pe mortar.

Metodele de conservare au probleme cu:
(A) indepartarea sarurilor rezultate prin patrunderea anionului SO
4
2-
prin mortar
- mediul inconjurator 2SO
2
+ 2H
2
O + O
2
2HSO
4
-
+ 2 H
+
2HSO
4
-
2 H
+
+ SO
4
2-
Ca
2+
+ SO
4
2-
CaSO
4


-echilibrul de disociere a sulfatului de calciu
,
K
sp
= 4.9310
5

- efectul de speciatie apare in cazul in care disociatia unei sari poate avea loc printr-o etapa intermediara mult mai
solubila se modifica solubilitatea sari ca atare. De exemplu

Formarea intermediara a HCO
3
-
duce la o crestere a solubilitatii CaCO
3
. In mod similar daca apare un agent complexant ca EDTA care sa
consume Ca
2+
solubilitatea CaCO
3
creste si mai mult.
,
Participarea la echilibru a hidroxidului de calciu foarte solubil favorizeaza aparitia efectului ionului comun conform principiului Le
Chatelier's Principle prin deplasarea inverse a echilibrului chimic. Deasemenea efectul de sare modifica prin adaugarea suplimentara a unei
saruri modifica taria ionica si coeficientii de activitate si se modifica solubilitatea. Efectul de faza se refera la reteaua cristalina a solidului supus
dizolvarii, de exemplu aragonite se dizolva diferit de calcite. Efectul marimii particulelor solubilitatea creste cu scaderea dimensiunii
particulelor tipic mai mici de 1 m. Acestea se cuantifica prin:

-
*
K
A
constanta de solubilitate, suprafata pe mol A, A=o, tensiunea de suprafata a unei particule dizolvate, A
m
suprafat molara de
solid (in m
2
/mol), R constanta universala a gazelor, T temperature absoluta. Efectul de temperature
Table of Solubility Products
Compound Formula Temperature K
sp

Data Source
(legend below)
Barium Carbonate BaCO
3
16C 710
9
C, L
Barium Carbonate BaCO
3
25C 8.110
9
C, L
Barium Oxalate dihydrate BaC
2
O
4
18C 1.210
7
C, L
Barium Sulfate BaSO
4
18C 0.8710
10
C, L
Barium Sulfate BaSO
4
25C 1.0810
10
C, L
Barium Sulfate BaSO
4
50C 1.9810
10
C, L
Calcium Carbonate calcite CaCO
3
15C 0.9910
8
C, L
Calcium Carbonate calcite CaCO
3
25C 0.8710
8
C, L
Calcium Carbonate calcite CaCO
3
18-25C 4.810
9
P
Calcium Chromate CaCrO
4
18C 2.310
2
L
Calcium Hydroxide Ca(OH)
2
18C-25C 810
6
P
Calcium Hydroxide Ca(OH)
2
25C 5.0210
6
w
1



In tabelul de mai sus sunt date constantele de solubilitate ale compusilor greu solubili de unde se poate vedea motivul pentru care CaSO
4

este mai solubil decat CaCO
3
si prin influenta umiditatii au loc precipitari si solubilizari repetate.
- In 1966 s-a propus "Barium Method," in care se aplica comprese de Ba(OH)
2
pentru indepartarea CaSO
4
.
Ba(OH)2(aq + CaSO4(s) BaSO4(s) + Ca(OH)2
Excesul de Ba(OH)2(aq este absorbit in intonaco si parte se carbonateaza consolidand moratrul si pigmentul
Ba(OH)2(aq + CO2 BaCO3(s) + H2O

- metoda compreselor pe hartie din orez cu [(NH4)2CO3]
Calcium Sulfate CaSO
4
10C 6.110
5
C, L
Calcium Sulfate CaSO
4
25C 4.9310
5
w
1

Cupric Carbonate CuCO
3
25C 110
10
P
Cupric Hydroxide Cu(OH)
2
18C-25C 610
20
P
Cupric Hydroxide Cu(OH)
2
25C 4.810
20
w
1

Ferric Hydroxide Fe(OH)
3
18C 1.110
36
C, L
Ferrous Carbonate FeCO
3
18C-25C 210
11
P
Ferrous Hydroxide Fe(OH)
2
18C 1.6410
14
C, L
Ferrous Hydroxide Fe(OH)
2
25C 110
15
; 8.010
16
P; w
2

Lead Carbonate PbCO
3
18C 3.310
14
C, L
Lead Chromate PbCrO
4
18C 1.7710
14
C, L
Lead Hydroxide Pb(OH)
2
25C 110
16
; 1.4310
20
P; w
1

Lead Sulfate PbSO
4
18C 1.610
8
C, L
Mercuric Sulfide HgS 18C 410
53
to 210
49
C, L
Zinc Hydroxide Zn(OH)
2
18C-20C 1.810
14
C, L
Zinc Sulfide ZnS 18C 1.210
23
C, L
data source legend: L=Lange's 10th ed.; C=CRC 44th ed.; P=General Chemistry by Pauling, 1970 ed.; w
1
=Web source 1; w
2
=Web source 2
CaSO4) + (NH4)2CO3(aq) [(NH4)2SO4(aq) + CaCO3(s) (4)

Intr-o lucrare de laborator trebuie determinate solubilitatile CaCO3, CaSO4, BaSO4

(B) interventii anterioare de conservare in care s-a acyionat asupra nuantelor prin cleiuri, uleiuri, ou, ceara. Aceste materiale organice s-au
deterirat primele si au fost hrana dezvoltarii populatiei bacteriene. Problematica o reprezinta indepartarea acestor resturi. Consolidarea picturii si
s stratului intonaco s-a facut prin injectarea unor solutii polimerice deoarece fresca continea cantitati mici de sulfati dar cantitati mari de azotati
iar Ba(OH)
2
este contraindicate.
Obtinerea unui esantion de fresca

Saptamana 1 (Ziua 1)
1. Mix the arriccio as two parts sand and one part slaked lime. (For two 2" x 2" tiles, measure out 50 ml of sand in a plastic beaker and then use
25 ml of slaked lime. Mix in 250-ml plastic beaker.) Mix well. You may need to add water if the lime sample was not
wet; on the other hand, the plaster will crack if it is too wet.
2. Obtain a tile which has been soaked in water overnight. Dry it until the surface is no longer shiny.
3. Apply the plaster evenly over the rough side of the tile to a thickness of about 3 mm, thinner that for an arriccio on a wall. Save a small
amount of the arriccio plaster for testing; label the beaker in which it was mixed and store until Week 2.
4, Let the plaster dry for 10 minutes; the tile will absorb the water.
5. Smooth the surface of the plaster with a spatula to give a relatively uniform surface.
6. Let the tile dry for a minimum of two days so that the plaster is converted to calcium carbonate (carbonation).

Between Day1 and Day 2. Preparation of the senopia. Sketch your picture on tracing paper (provided). Use a tracing a pin to perforate the paper along the lines of your sketch. Plan the color
scheme for your fresco and list pigments appropriate for it. (Large fresco wall paintings begin with a rough sketch on the arriccio. This sketch is then transferred to paper.)


(Ziua 2) Preparation of the intonaco and giornata.
1. Mix the intonaco as one part slaked lime and one part finely powdered sand. (For a two 2" x 2" tile, measure out 35 ml each of sand and of
slaked lime. Mix in 250-ml plastic beaker.)
2. Thoroughly wet the arriccio and the tile. Then spread the plaster evenly to a thickness of about 2 mm. Let the tile dry about ten minutes.
3. "Polishing" the intonaco orients the sand and gives a smooth, polished surface. Smooth the surface in a single direction with a large, clean
spatula. Remove any large granules that pop up and replace any miss plaster.
4. Apply a small brush stroke of water to ascertain if the surface is ready for painting. If the plaster readily absorbed the water, it is dry enough
for painting.
5. Transfer the outline of your picture onto the plaster surface by laying the sinopia on the tile and pouncing with a lime-compatible pigment.
Instead of pouncing, you may wish to gently incise the drawing into the plaster through the tracing paper.
6. Select the pigments and prepare them for painting by grinding a small amount in distilled with a flat spatula on a glass plate. The pigment
preparation is ready when a small amount, dropped into water, mostly floats and does not sink. The pigment is applied as a dilute wash.
7. If you have prepared more than one tile, number each and record the name and formula of pigments used for each in your notebook. Paint a
strip of the pigment for color reference as well.
8. Paint the tile. Shading with dark pigments is done first and then over-painted with lighter pigments. Since the colors are transparent, several
thin layers of paint are needed to obtain bold colors. Wait 10 or 14 minutes between color layers to ensure that they do not mix.
9. When the painting has been completed, set the finished tile in a plastic bag, but leave the top open. (This procedure will ensure that the tile
drives slowly and will minimize or eliminate crack formation.) Let the tile cure so for several days to consolidate the pigment with the newly
formed calcium carbonate matrix of the fresco, a permanent and colorfast art object for generations to come.
Chemistry of Frescoes (Week 1 or 2)
A. Acid-base Chemistry. Use pH test papers as demonstrated by the instructor.
1. Chip a piece of the intonaco/arriccio from a sample fresco tile or from your hardened excess arriccio plaster and put it in a disposable test
tube. Carefully add a drop of 3 M HCl to it. Repeat with a sample of fresh lime plaster.
2. Determine the pH of the slaked lime and pure CaCO3 suspended in water.
3. Add a pinch of calcium oxide to a disposable test tube. Add about 1 ml to the test tube and test it for heat evolution. Determine the pH of the
resultant mixture.
4. Add about 20 ml of water to a 100-ml plastic beaker. Measure the pH of the water.Carefully add crushed dry ice, solid CO2, to the beaker.
After most of the solid has disappeared, measure the pH again. Write equations for any reactions that occurred above and discuss the results of
the pH tests.
B. (Week 1) Evaluation of the relative solubilities of CaCO
3
, CaSO
4
, and BaSO
4
.
Dissolution of these salts can be represented generically as follows:
MX(s) M2+ (aq) + X2-+(aq) (7)
The calcium and barium ions are represented by M2+ and the carbonate and sulfate ions, by X2-. In this experiment, students will prepared
saturated solutions of each of the three salts and determine the amount dissolved by measuring the concentration of the cation, M2+ (aq), in this
solution. This measurement will be done by following the reaction of the cations with the reagent EDTA whose structure is shown below.

EDTA
Although EDTA appears to have a complicated structure, it can be represented by Y4- as shown in the following equation for its reaction with
cations: M2+ + Y4- MY2- (7) 6 The reaction of EDTA with either calcium or barium ions will be followed by a process called titration in which
an indicator changes color when the number of moles of EDTA molecules (in an aqueous solution) added equals that of the cations. Students
will practice their titration technique with a solution of known calcium ion concentration.
Procedure (Students will work in pairs).
1. Preparation of saturated solutions of CaCO
3
, CaSO
4
, and BaSO
4
. Use a spatula to transfer an amount equivalent to about 2 teaspoons of each
solid to each of three separate 50 ml capped centrifuge tubes. Add approximately 40 ml of distilled water. Put the 3 tubes on the wrist-action
shaker and shake vigorously for at least a half-hour. Remove the tubes from the shaker and allow the undissolved solid to settle to the bottom of
the tube. The aqueous layers are saturated with the appropriate salts. 2. Titration procedure. Note that each student pair will do four sets of 3
titrations: From the Ca2+ standard and from the three saturated solutions (CaCO3, CaSO4, and BaSO4). Working with standard. Pour about 20
ml of the Ca2+ standard ( 2.50 x 10-3 M) into a labeled 50 ml plastic beaker. In a separate labeled 50 ml plastic beaker, pour 20 ml of 1.5 x 10-2
M EDTA Obtain and label a 5 ml syringe (with needle): "Calcium standard." The most efficient and convenient form for organizing your
titration is a table. Here is a suggested format (report the exact concentration of EDTA):
Table 1. Titration of Ca2+ standard (2.50 x 10-3 M) with 1.5 x 10-2 M EDTA
Trial 1 Trial 2 Trial 3
Sample Weight, grams Weight, grams Weight, grams
Empty Bottle
Bottle + standard
Bottle + standard + reagents
Bottle + standard + reagents +
EDTA
a. Weigh a small titration bottle and record its weight (or if no others students are using the same balance, tare the bottle.)
b. Remove the bottle from the balance, and use the 5 ml syringe to add between 4 and 5 ml of the calcium standard to the bottle. Weigh the
bottle again to determine the exact amount of calcium standard added.
c. Add 2-3 drops of the pH 10 ammonia buffer and 1 drop of the Calmagnite indicator to the titration bottle and weigh the bottle again. The
solution should be red at this point.
d. Remove the bottle from the balance. Take a disposable Pasteur pipette and add the EDTA solution dropwise to the bottle and swirl it carefully
after each addition. Continue to add EDTA until the solution turns blue. This point is called the endpoint in the 7 titration and signals that all the
Ca2+ has reacted with EDTA. Weigh the bottle to determine the exact amount of EDTA added.
e. Dispose of the solution in the titration bottle and wash it with distilled water. Repeat the procedure at least three times or until you are onfident
of your titration skills. In order to evaluate these skills, you will need to do some arithmetic calculations: The simplest way to check your skills is
to calculate the number of grams of EDTA solution/grams of Ca2+ solution for each trial. They should be nearly the same for all three titration
trials. Determining the concentration of M2+ (as a measure of solubilities) in saturated solutions of salts. The titration procedure is nearly
identical to that used for the calcium standard. For these solutions, it is necessary to filter them to ensure that no solid is transferred. After filling
a syringe (use a separate labeled syringe for each solution) with solution, remove the needle and attach a 0.45 m disposable filter to the
syringe. Push the solution through this filter into the titration bottle. The same filter may be used for all the titration trials for a particular
solution. Record the weights at all stages in the titration. If you find that the amount of EDTA used is too small to measure accurately for any
of the solutions, you may wish to do additional titration trails with a more dilute (1.25 x 10-3 M) EDTA solution.
Analysis of titration data to evaluate relative solubilities.
1. Organize the titration data in a table similar to the one below (with similar entries for the solutions of CaSO4 and BaSO4):
Sample and Trials Trial 1 Trial 2 Trial 3
grams grams grams
A. Saturated solution of CaCO3
Weight of Sample
Weight of EDTA used
Weight of EDTA/Weight of sample
Moles of M2+ in solution
2. From the titration results [average of the three values for Weight of EDTA/Weight of sample), determine the relative solubilities of the three
compounds. Which one is the most soluble? The least soluble?
3. From number of moles of M2+ (average of three trials), express the solubilities in moles/liter, grams/liter, and grams/100 ml. Compare your
results with values you find in the CRC Handbook (Note that the CRC Handbook includes numerical values for solubilities in g/100 mL only in
editions before 1998.).
4. Conclusions. Write a short paragraph summarizing your findings regarding the solubility of these three salts and the implications of your
findings for the protection of outdoor monuments carved in limestone (CaCO3) from the detrimental effects of acid rain, primarily dilute
solutions of sulfuric acid.
D. Effects of acid rain on Frescoes (Optional, extra credit). Devise and carry out an experiment to test the effects of dilute solutions (1 x 10-3
or 1 x 10-4 M) of HCl and H2SO4 (acid rain) on the stability of fresco paintings. Dilute acid solutions will be available.



Acidul silicic si silicatii


Raza ionului de Si
+4
raportata la raza anionului de O
-2
cere o coordinare tetraedrica a ionului de Si
+4
cu 4 O
-2
.
Acest tetraedru se poate lega de alte tetraedre prin varfuri, laturi sau fete generand diferite grupe de silicate

Variante de acizi silicici care se obtin indirect
H
2
Si
2
O
5
H
2
SiO
3
H
4
SiO
4
H
6
Si
2
O
7
Acid pirometasilici Acid metasilicic acid ortosilic acid piroorto silicic
Silicatii ( liniari si ciclici )
Si
2
O
5
2-

SiO
3
2-

SiO
4
4-

Si
2
O
7
6-
Pirometasilicati metasilicati ortosilicati piroortosilicati





Pirometasilicati
Si
2
O
5
2-

Metasilicati SiO
3
2
Ortosilicatii SiO
4
4-

Piroortosilicatii
Si
2
O
7
6-

Structuri stratificate Liniari (SiO
3
-2
)
n
Ciclici (Si
n
O
3 n

)
m-
Polimerici Si
4
O
11
-6







exemple
- mica
- argilele
- talcul


Mg
3
[(Si
2
O
5
)
2
(OH)
2
].
- piroxenii
- orhopiroxenul
amphibole
(Mg,Fe)SiO
3
.
Eustatita
MgSiO
3
.
Diopsidul
(Mg,Ca)SiO
3
.
-3-unitati (Si
3
O
9
)
6-
, -
benitoite.
-4-unitati (Si
4
O
12
)
8-
,
axinite.
-6-unitati (Si
6
O
18
)
12-
,
beryl Al
2
Si
6
O
18
.



-azbestul
Mg
6
[(Si
4
O
11
)(OH)
6
].H
2
O
-olivina
(Mg,Fe)
2
SiO
4

-zirconul ZrSiO
4

-grenatele contin
cationic bivalenti si
trivalenti si anioni straini
Topazul
Al
2
[F
2
(SiO
4
)]



thortveitita
Sc
2
Si
2
O
7






Silicatii din scoarta terestra

Exemplul cel mai bun feldspatul, zeolitii, ultramarinul.
In cazul in care tetraedrele T
d
de SiO
4
se unesc prin varfuri atunci unitatea structurala este - SiO
2
(quartz, cristobalite, and tridymite).
In cazul T
d
de SiO
4
sunt inlocuiti si alterneaza in parte cu T
d
AlO
4
atunci deficitul de sarcina se completaeza cu alti cationi.
Formula generala a unui silicat natural X
m
Y
n
(Z
p
O
q
) W
r

X = K
+
, Rb
+
, Ba
+2
, Na
+
, and Ca
+2
cationi mari cu NC = 8-12.
Y = Al
+3
, Mg
+2
, Fe
+2
, Fe
+3
, Mn
+2
, and Ti
+4
cationi cu numar de coordinare NC = 6..

Z = unitatea T
d
(SiO
4,
AlO
4
). p:q = depinde de gradul de polimerizare al tetraedrelor si dau valorile pentru m, n, and
W = (OH
-
) sau F
-
, Cl
-
r echilibrarea sarcinii;
Exemple :
topazul Al
2
[SiO
4
(F,OH)
2
], Ultramarinul este mineral complex ce contine ca ion de compensatie sulf Na
8-10
Al
6
Si
6
O
24
S
2-4

Lapis lazuli este o rocka, si nu un mineral deoarece contine mai multe minerale. Principalul component al rocii de lapis lazuli este lazuritul
sau azuritul (25% to 40%), care este un silicat natural (Na,Ca)
8
(AlSiO
4
)
6
(S,SO
4
,Cl)
1-2
.

plus alti constituenti calcite (white), sodalite (blue),
pyrite (metallic yellow). si augite, diopside, enstatite, mica, hauynite, hornblende, and nosean. Cateva specii contin sulfur imbogatit in lllingite
varietate geyerite. Lapis lazuli apare si in forme cristaline de marmura ca urmare a procesului de contact metamorphism.

Tehnologia silicatilor
Cimentul
In insula Portland din Dorset, Anglia exista o piatra de constructie numita Piatra de Portland.Joseph Aspdin, din Leeds, a elaborate un brevet
pentru fabricarea cimentului pe care l-a numit ciment Portland asemanator in proprietati cu cimentul "Roman cement" patentat in 1796 de James
Parkerc. Aspdin's son William, in 1843, a produs o versiune modificata iar in 1853 obtine o fermula imbunatatita si pleaca in Germania, devine
producator de ciment si in 1878 guvernul germane mite un standard.
Compozitia cimentului Portland
Portland cement clinker is a hydraulic material which shall consist of at least two-thirds by mass of calcium silicates (3CaO.SiO
2
and
2CaO.SiO
2
), the remainder consisting of aluminium- and iron-containing clinker phases and other compounds. The ratio of CaO to SiO
2
shall
not be less than 2.0. The magnesium content (MgO) shall not exceed 5.0% by mass.
Ceramica

Caramida
Fresca - problematici






HNO
2

Forma trans in spectrul de microunde trans cis
Preparation
Saruri + acizi NaNO
2
+ HCl HNO
2
+ NaCl

Proprietati fizice se cunoaste numai sub forma de solutie
Proprietati chimice descompunerea redox prin disproportionare 2 HNO
2
NO
2
+ NO + H
2
O
- obtinerea sarurilor de diazoniu HNO
2
+ ArNH
2
+ H
+
ArN
2
+
+ 2 H
2
O
Nitritii

Nitritul de sodium NaNO
2
este folosit ca si fixative de culoare si conservant pentru carne si peste, ( E250. KNO
2
E249) is used in the same
way.solubil si hygroscopic si se oxideaza incet in atmosfera de oxygen pana la nitrate. In cantitate mare se foloseste in obtinerea diazoderuvatilor
si nitrozocompusilor, inhibitor de coroziune,. Se utilizeaza ca vasodilatator si brohodilatator. Nitritii sunt produsi rezultati in metabolismul
hepatic iar cantitatile suplimentare introduce prin alimentatie oxideaza Fe
2+
la Fe
3+
impiedicand astfel transportul oxigenului. Acest fapt este
cunoscut ca metemoglobinemia si duce la scaderea cantitatii de oxygen din tesuturi. Antidotul este albastrul de metilen care readuce Fe
3+
la Fe
2+
Acidul azotic HNO
3


Este cel mai important compus oxigenat al azotului dat fiind importanta practica deosebita prin utilizarea sa in:
ingrasaminte; explosives, metalurgie,
Obtinere industriala ( metoda speciala ) Obtinere in laborator ( metoda generala )
N
2
+ H
2
2NH
3
H
2
SO
4
+ NO
3
HSO

4
(s) + HNO
3
(g)

NH
3
+ O
2
NO + H
2
O
NO + O
2
NO
2

NO
2
+ H
2
O HNO
2
+ HNO
3

HNO
2
HNO
3
+ NO + H
2
O

Proprietati fizice si chimice
HNO
3
In stare pura ca lichid incolor da reactii de autoprotoliza 2 HNO
3
NO2 + NO3 + H2O, In timp acidul devine galben din cauza
unei reactii fotochimice 2 HNO3 NO2 + O2 + H2O. Este mai greu decat apa de 1.5 ori, densitatea este 1.513 g cm
-3
at 20
o
C. p.f. 86
o
C,
solubil in apa in orice proportie. Solutia poate fi concentrata pana la maxim 68%. Ajungand la un azeotrop cu p.f. 121
o
C. Poate fi concentrat prin
alte metode: 1) prin trecerea dioxidului de azot prin solutia concentrate de 68% aqueous solution si apoi distilat in prezenta acidului sulfuric pana
la 98% concentration can be obtained. 2) prin racirea acidului concentrate la -42
o
C, se depun cristale incolore de acid azotic.



Proprietati chimice generale si particulare





Azotatii
NO
3
-
Toate elementele metalice formeaz azotati, toti azotatii sunt solubili si higroscopice si au urmatoarele caracteristici:
M(NO
3
)
2
. 6 H
2
O, M(NO
3
)
3
. 9 H
2
O, M(NO
3
)
3
M(NO
3
)
2
. H
2
O azotati dubli care seamana cu alaunii
Anionul nitrate are o geometrie trigonal plana, izoelectronic cu anionul carbonat.

Azotatul de sodiu NaNO
3
cunoscut ca Chile saltpeter sau Peru saltpeter solid alb, solubil in apa. Este utilizat ca un ingredient in fertilizatori,
pirotehnica, conservant alimentar E251, propulsor de rachete, obtinerea emailurilor.

.





Acizii fosforului

Acizii fosforici
Acid metafosforic Acid ortofosforic Acid pirofosforici
H
3
POn H
3
POn H
4
P
2
On
meta fosforic fosforic Piro-fosforic hipofosforic
HPO
3
H
3
PO
4
H
4
P
2
O
7
H
4
P
2
O
6

+5 +5 +5 +4

P
O
O H
O








-este un acid care se
prezinta ca un lichid
incolor siropos, fara
miros, hygroscopic,
foarte solubil in apa,
dietil eter si alcool
etilic si se obtine:
Na
2
HPO
4
Na
4
P
2
O
7
+ H
2
O

Na
4
P
2
O
7
+ 2Pb(NO
3
)
2

Pb
2
(P
2
O
7
) + 4NaNO
3

Pb
2
(P
2
O
7
) + H
2
S 2PbS +

H
2
P
2
O
7

2Na
2
HPO
4
Na
4
P
2
O
4
+
H
2
O
- hidrolizeaza usor
H
4
P
2
O
7
+ H
2
O 2H
3
PO
4

RECUNOSTERE
Na
4
P
2
O
4 +
[Co(NH
3
)
6
]
4
(P
2
O
7
)
3

Polimerii metafosforici Acizii polifosforici


n H
3
P
3
O
9
3HPO
3
n H
3
PO
4
- (n-1) H
2
O H
(n+2)
P
n
O
(3n+1)

H
3
P
3
O
9
H
5
P
3
O
10

ciclici aciclici







P
O
HO O
OH
H
n



I II III IV V VI
obtinere Polimerizarea
nHPO
3
gradul de
polimerizare este in
functie de conditii

(NH
4
)
2
HPO
4
HPO
3
+2NH3 + H2O
H
4
P
2
O
7
+ POCl
3
5
HPO
3
+ 3HCl
Istoric: P
4
+HNO
3

P
2
O
5
+H
2
O
P
4
+O
2

PX
5
+H
2
O
P
4
+O
2
+H
2
OH
2
P
2
O
6
(NaOH)
Na
2
H
2
P
2
O
6
.6H
2
O
P
4
+NaClO+H
2
O
H
2
P
2
O
6
+NaCl
P
4
+NaOH+H
2
O
2

H
2
P
2
O
6
+NaCl
Ca
5
[(PO
4
)
3
(OH)
2
]+ H
2
SO
4
H
3
PO
4
30-45%
comercializat ca fertilizator

Proprietati
fizice
- cunoscut ca sticla
fosforica,ca solid
sticlos,
-acid monobasic tare,
- solid alb care se topeste la
42.35
0
C intr-un lichid
viscos
-Proaspat topit are
conductibiitate electrica
datorita autoprotolizei:
2H
3
PO
4
H
2
PO
4
-

+ H
4
PO
4
+

- foarte solubil in
apa si se comporta
ca acid tare
Proprietati polimerizeza Prin deshidratare
chimice trece in acid
fosforic
IR

identificare Ca guaniina
hipofosfat sau ca
Th(P
2
O
6
)
utilizari 80% se foloseste ca
ingrasamant, 10%
detergenti, insecticide
production


SARURI - se obtin prin
deshidratarea
fosfatilor diacizi si
a pirofosfatilor si
din KCl cu HPO
3


Metafosfatii sunt
polimeri
Sunt instabili in
medii alkaline
(MPO
3
)
n
+ NaOH
MPO
3+
H
2
O
Insolubili
metafosfatii de Ag,
Ba, Pb

Fosfatii
Sunt importante sarurile
lor ca schimbatpri de ioni

Fosfatii

H
2
PO
4
-
HPO
4
2-
PO
4
3-
Fosfatii naturali sunt ortofosfati, fluoro si hidroxiapatite;
Fosfati insolubili: Ca
3
(PO
4
)
2
, Ag
3
PO
4,
FePO
4,
Pb
3
(PO
4
)
2
fosfati cu importanta comerciala:
(NH
4
)
3
PO
4
- ingrasamant
NaH
2
PO
4 ,
Na
2
HPO
4
,

NaH
2
PO
4 ,
(NH
4
)H
2
HPO
4
,

(NH
4
)Na HPO
4
.4 H
2
O saruri fosforice utilzate in chimia analitica,
Na
3
PO
4 .
6 H
2
O pentru epurarea apei

Recunoastere PO
4
3-
+ (NH
4
)MoO
4
+ 3H
+
(NH
4
)
3
[P(Mo
3
O
10
)
4
] + H
2
O fosfomolibdatul de amoniu de culoare galbena
Fosfatii organici au o importanta bilogica majora. Fosfatii de zahar sunt importanti pentru foto.sinteza, energia asociata hidrolizei legaturilor C-
O-P are o importanta fundamentala in sistemele bilogice ca esteri ai glucozei cu acidul fosforic.






Acizii fosforosi
HPO
2
H
3
PO
2
H
3
PO
3
H
4
P
2
O
5

metafosforos hipofosforos fosforos Piro-fosforos
+1 +3 +3
I II III IV


P
O
O
H


I II III IV
obtinere PH
3
+ O
2
HPO
2
+ H
2
P
4
+ Ba(OH)
2
+ H
2
O
PH
3
+ Ba(H
2
PO
2
)
2

PCl
3
+ H
2
O H
3
PO
3
+ HCl PCl
3
+ H
2
O + H
3
PO
3

H
4
P
2
O
5
+ HCl
Prin agitare 5 h
Proprietati
fizice
Solid incolor solubil in apa Lichid incolor uleios, solubil
in apa
Substanta cristalina si putin stabile
termic
Proprietati
chimice
Se oxideaza cu (I
2
, HNO
3
, H
2
SO
4
,
SO
2
, Cu
2+
) in H
3
PO
4

Character reducator
Disproportioneaza
H
3
PO
3
H
3
PO
3
+ PH
3
Se oxideaza cu (HNO
3
,

H
2
SO
4
, AgNO
3,
in H
3
PO
4

IR
identificare
utilizari Analiza Se si Te
SARURI hipofosfitii fosfitii
Ca, Fe, Na, sunt folosite ca tonici
in medicina
Na, K, Ca, solubili si stabili in
aer


Acidul sulfuros ( N.O.= +4) H
2
SO
3


Acidul sulfuros este foarte instabil in solutie unde apare in echilibrele de dizolvare a dioxidului de sulf SO
2
+ H
2
O HSO
3

+ H
+
K
a
=
1.54 10
2
; pK
a
= 1.81. dar poate fi detectat in faza gazoasa si da saruri stabile
sulfitii acizi HSO
3

-
(bisulfitii) si sulfitii neutri SO
3

2-
.
SO
2
+ NaOH NaHSO
3

Na
2
SO
3
SO
2

+
Na
2
CO
3
NaHSO
3
NaHS
2
O
5
+
H
2
O
-
NaHCO
3
+
SO
2
+
NaOH
-
H
2
O
acid +
SO
2
+
Zn
+
SO
2
Na
2
S
2
O
4

+
ZnO
oxidare
Na
2
SO
4
+
S
Na
2
S
2
O
3
Descompunerea
termica




Descompunerea termica este o problema specifica obtinerea industriala Ca(HSO
3
)
2
SO
2
+ CaCO
3
+ H
2
O

Na
2
SO
3
Na
2
SO
4
+ Na
2
S 600
0
C
2NaHSO
3
Na
2
S
2
O
5
+ H
2
O evaporare
MgSO
3
MgSO
4
+ MgS
2
O
3
+ MgO 300
0
C
MgSO
3
MgO + SO
2
600
0
C















Acidul sulfuric (N.O. = +6) H
2
SO
4


Descoperit de Johann Van Helmont in1600 prin distilarea distructiva a sulfatului feros.
Obtinere numai in USA se produc anual 40 millioane tone dintre care 65% sunt orientate spre obtinerea de ingarsaminte agricole. Obtinerea se
poate face prin cele doua metode majore la nivel industrial:
(i) procedeul camerelor cu Pb se obtin solutii 62% to 78% H
2
SO
4
si
(ii) procedeul prin contact ; Ambele procede folosesc arderea SO
2
la SO
3
urmata de dizolvarea acestuia in apa. Prin urmare
partea comuna a celor doua metode este obtinerea SO
2
, care se poate realize industrial astfel;
S(s) + O
2
(g) SO
2
(g)
4 FeS(s) + 7 O
2
(g) 2 Fe
2
O
3
(s) + 4 SO
2
(g)
2 H
2
S(g) + 3 O
2
(g) 2 SO
2
(g) + 2 H
2
O(g)
2 SO
2
(g) + O
2
(g) 2 SO
3
(g) Reactia de oxidare a SO
2
are o viteza foarte mica motiv pentru care are nevoie de catalizator:
(i) in metoda camerelor cu Pb catalizatorul este NO
2
In turnurile Glover se sulfa aer si NO si se stropeste apa si au loc reactiile:
2 NO + O
2
2NO
2

SO
2
+ NO
2
+ H
2
O H
2
SO
4
+ NO
(ii) in procedeul prin contact catalizatorul este V
2
O
5
, amestecat cu sulfati ai metalelor alkaline si pus pe un pat de silice. SO
3
gazos este apoi
dizolvat in apa
SO
3
(g) + H
2
O(l) H
2
SO
4
(l) si da o solutie 98% H
2
SO
4
.
Proprietati fizice
H
2
SO
4
este un lichid incolor, indoor, uleios, ingheata la 10.5C. fumega la incalzire pentru ca se descompune in H
2
O si SO
3
. Solutia se poate
concentra prin distilare pana la 98.33%. cand devine azeotrop. P.f. 338C si datorita afinitatii pentru apa este folosit ca agent de uscare de
exemplu in indepartarea apei din zahar C
12
H
22
O
11
si carbonizeaza si alte materiale organice (hartie, oase, plante ).
C
12
H
22
O
11
+ nH
2
SO
4
--> 12C + (11H
2
O + nH
2
SO
4
)

CH
3
CH
2
OH + nH
2
SO
4
--> CH
2
= CH
2
+ (H
2
O + nH
2
SO
4
)

Solutiile de acid sulfuric pot fi diluate numai prin adaugarea acidului peste apa rece dat fiind caldura de dizolvare mare a hidratilor formati
H
2
SO
4
.nH
2
O

Proprietati chimice
H
2
SO
4
anhidru este foarte polar si are o constanta dielectrica de 100 dat fiind procesul de autoprotoliza:
2 H
2
SO
4
H
3
SO
+4
+ HSO
4
constanta de autoprotoliza fiind mult mai mare decat a apei K
ap
(25C)= [H
3
SO+4][HSO4] = 2.710
4
.
In ciuda viscozitatii constanta dielectrica este mare dat fiind mecanismul schimbului protonic intramolecular , in solutii 100% H
2
SO
4
exista
foarte multe specii HSO
4
(15.0), H
3
SO
+4
(11.3), H
3
O
+
(8.0), HS
2
O
7
(4.4), H
2
S
2
O
7
(3.6), H
2
O (0.1).










Acid sulfuric oleum 25%, 45% este o solutie 98% in care se dizolva SO
3
si se formeaza acidul pirosulfuric H
2
S
2
O
7
care da si saruri solubile
Na
2
S
2
O
7
, NaHS
2
O
7.







SULFATII ( SO
4
2-
) si Sulfatii acizi sau bisulfatii ( HSO
4
-
)

Sulfates
Sulfatii sunt saruri transparente sau translucide, majoritatea colorati si solubili in apa. Se pot clasifica in sulfati anhidri , hidratati si sulfati
insolubili.
Sodium sulfate anhidru Na
2
SO
4
este cunoscut ca mineralul tenardita, iar sarea hidratata Na
2
SO
4
10H
2
O Glauber's salt sau mirabilita.
- este o sare stabile si rezistenta la oxidare, si da un echilibru cu acidul sulfuric Na
2
SO
4
(aq) + H
2
SO
4
(aq) 2 NaHSO
4
(aq)
- este o sare tipic ionica, poate precipita ionii de Ba
2+
si Pb
2+
, este solubila in apa cu o solubilitate care devine independenta de temperature la
32.384 C :
Na
2
SO
4
(aq) + BaCl
2
(aq) 2 NaCl(aq) + BaSO
4
(s)


Obtinere industriala

2 NaCl + H
2
SO
4
2 HCl + Na
2
SO
4

4 NaCl + 2 SO
2
+ O
2
+ 2 H
2
O 4 HCl + 2 Na
2
SO
4

UTILIZARI - procedeul Kraft pentru procesarea pulpei de lemn. Industria sticlei pentru indepartarea bulelor de aer din sticla topita, industria
textile, drying agent, pentru solutii organice,
Sulfati mai importanti
Vitriolii sulfatii unor ioni metalici bivalenti ai Mg, Mn, Fe, Co, Ni, Zn, Cu cristalizati si hidratati cu 7 molecule de H2O cu exceptia
CuSO4.5H2O;
Alaunii sulfati dubli ai ionilor metalici monovalenti Na
+
K
+
Rb
+
Cs
+
NH
4
+
Tl
+
( cu exceptia Li
+
, Cu
+
, Ag
+
, Hg
+
) si trivalenti Al
3+
Ga
3+
In
3+

Ti
3+
V
3+
Cr
3+
Mn
3+
Fe
3+
Co
3+
Rh
3+
Ir
3+
( nu Ln
3+
, Bi
3+
) cu formula generala M
I
M
III
(SO
4
)
2
.12H
2
O. Acesti sulfati sunt stabili in stare solida iar in
solutie se comporta ca un amestec de doi componenti. Importanta alanilor
Cosmetica
Alum in block form (usually potassium alum) is used as an aftershave, rubbed over the wet, freshly shaved face.
Styptic pencils containing aluminium sulfate or potassium aluminium sulfate are used as astringents to prevent bleeding from small
shaving cuts.
Alum was used as a base in skin whiteners and treatments during the late 16th Century. A recipe for one such compound was given thus :
Alum may be used in depilatory waxes used for the removal of body hair, or applied to freshly waxed skin as a soothing agent.
In the 1950s, men sporting crewcut or flattop hairstyles sometimes applied alum to their front short hairs as an alternative to pomade.
When the hair dried, it would stay up all day.
Alum's antibacterial properties contribute to its traditional use as an underarm deodorant. It has been used for this purpose in Europe;
Mexico; Thailand, where it is called Sarn-Som; throughout Asia; and in the Philippines, where it is called Tawas. Today, potassium alum
is sold commercially for this purpose as a "deodorant crystal," often in a protective plastic case.
Medicinal
Alum is used in many subunit vaccines as an adjuvant to enhance the body's response to immunogens. Such vaccines include hepatitis A,
hepatitis B and DTaP.
Alum in powder or crystal form, or in styptic pencils, is sometimes applied to cuts to prevent or treat infection.
Powdered alum is commonly cited as a home remedy for canker sores.
Preparations containing alum are used by pet owners to stem bleeding associated with animal injuries caused by improper nail clipping.
Alum is listed as an ingredient of some brands of toothpaste or toothpowder.
Culinary
Alum powder, found in the spice section of many grocery stores, may be used in pickling recipes as a preservative to maintain fruit and
vegetable crispness.
Alum is used as the acidic component of some commercial baking powders.
Alum was used by bakers in England during the 1800s to make bread whiter
[1]
. In 1875, the Sale of Food and Drugs Act prevented this
and other adulterations.
[2]

Flame retardant
Solutions containing alum may be used to treat cloth, wood and paper materials to increase their resistance to fire.
Alum is also a component of foamite, used in fire extinguishers to smother chemical and oil fires.
Chemical flocculant
Alum is used to clarify water by neutralizing the electrical double layer surrounding very fine suspended particles, allowing them to
flocculate (stick together). After flocculation, the particles will be large enough to settle and can be removed.
Alum may be used to increase the viscosity of a ceramic glaze suspension; this makes the glaze more readily adherent and slows its rate
of sedimentation.
Alum is an ingredient in some recipes for homemade modeling compounds intended for use by children. (These are often called "play
clay" or "play dough" for their similarity to "Play-Doh", a trademarked product marketed by American toy manufacturer Hasbro).
Descompunerea termica a sulfatilor
- sulfatii metalelor alkaline se descompun la temperature inalta fara descompunere
Na
2
SO
4
897
0
C, K
2
SO
4
1074
0
C

- sulfatii metalelor alcalino-pamantoase si tranzitionale se descompun la temperature inalta
CaSO
4
CaO + SO
3
1000
0
C
2 BaSO
4
2 BaO + 2 SO
2
+ O
2
1500
0
C
Fe
2
(SO
4
)
3
Fe
2
O
3
+ SO
3
500
0
C


Oxoacizii halogenilor
Oxoacizii si sarurile
1+ 3+ 5+ 7+
HClO HClO
2
HClO
3
HClO
4

Hipocloros cloros cloric percloric

ClO
-
ClO
2
-
ClO
3
-
ClO
4
-

Hipoclorit clorit clorat perclorat
HBrO HBrO
3
BrO
-
BrO
3
-
1+ 5+ 7+
HIO HIO
3
HIO
4

IO
-
IO
3
-

IO
4
-

Sunt instabili, disproportioneaza, se cunosc sub forma de saruri, mai importanta KClO
3


HClO
4
ClO
4
-
- obt: saruri KClO
4
+ H
2
[SiF
6
]

HClO
4
+ M


HClO
3
KClO
3

- structura, leg de hidrogen izomorfism, ins

HClO HClO
2
HClO
3
HClO
4
stabilitate, character acid, character oxidant

ClO
-
aq/OH
ClO
2
-

aq/neutru
ClO
3
-

topitura
ClO
4
-
topitura

Character oxidant
HClO
3
, cid tare (pK
a
1) oxidant.
obtinere:
Ba(ClO
3
)
2
+ H
2
SO
4
2HClO
3
+ BaSO
4

3HClO HClO
3
+ 2 HCl
8HClO
3
4HClO
4
+ 2H
2
O + 2Cl
2
+ 3 O
2

3HClO
3
HClO
4
+ H
2
O + 2 ClO
2


Cloratii
Anionul clorat si structura de rezonanta:

Obtinere in laborator
3 Cl
2
+ 6 KOH 5 KCl + KClO
3
+ 3 H
2
O
Obtinere industriala
3 Cl
2
+ 6 NaOH 5 NaCl + NaClO
3
+ 3 H
2
O
Potassium chlorate is used in chemical oxygen generators (also called chlorate candles or oxygen candles), employed as oxygen-supply systems
of e.g. aircraft, space stations, and submarines, and has been responsible for at least one plane crash. A fire on the space station Mir was also
traced to this substance. The decomposition of potassium chlorate was also used to provide the oxygen supply for limelights.
Potassium chlorate is used also as a pesticide. In Finland it was sold under trade name Fegabit.
Potassium chlorate can react with sulfuric acid to form a highly reactive solution of chloric acid and potassium sulfate:
2 KClO
3
+ H
2
SO
4
2 HClO
3
+ K
2
SO
4

When sugar is added to this reaction, it burns:
8 HClO
3
+ C
12
H
22
O
11
11 H
2
O + 12 CO
2
+ 8 HCl


Reactii utilizate in pirotehnica

KClO
3
+ C (S, Al )

KCl + CO
2
, (SO
2 ,
Al
2
O
3
)

HIO / IO- HIO
3
/ IO
3
-


HIO
4



+H
2
O
HIO
4
IO
4
-
IO
4
-
2(H
2
O) + H
+
H
5
IO
6
H
7
IO
7
saruri
Ac meta periodic ac paraperiodic ac orto periodic
2 H
5
IO
6
(Oh) H
4
I
2
O
9

- 3 H
2
O ac. Dimezoperiodic





HIDRACIZII
structura hidracizii corespund structurilor liniare si respectiv structurilor unghiulare

Descriere
H - F 0.95 formeaza cristale ortorombice cu molecule associate prin legaturi de hydrogen in forma de zig-zag in
stare lichida moleculele sunt associate in formatiuni de 5-6 molecule. Solutii concentrate de fluoruri, F

in acid fluorhidric formeaza


anionul diflorura [HF
2
]

cu structura F H F in care F..F este de 2.26 A


0
spre deosebire de legatura de hydrogen F H.F in care
distanta dintre atomii de F este de 2.55 A
0
, dat fiind legatura tricentruca din anionul de diflorura fapt care se observa si din energiile de
legatura:
E
H-F

(HF)n
= 6.7 kcal/mol E
[HF2]
= - 27 kcal/mol
HF
g
(HF)n [HF2]
IR F-H 4140 cm
-1
3440 cm
-1
1450 cm
-1

H - Cl este o molecula covalenta polara care-I ofera posibilitatea dizolvarii in solventii polari.
H - Br este un gaz neinflamabil cu miros intepator, fumega in atmosfera umeda, formeaza cu apa solutii saturate cu concentratie 47.38% HBr si
un azeotrop cu temperature de fierbere de 126C. Boiling less concentrated solutions releases H
2
O until the constant boiling mixture
composition is reached.
H - I este un gaz incolor care fumega in atmosfera umeda, este exceptional de solubil in apa.
Toti hidarcizii grupei VII sunt foarte solubili in apa in proportie de 450 volume de hidracid gazos / 1 litru de apa. procesul de dizolvare nu
respecta legea Henry presiunea partiala a unui gaz de deasupra solutiei sale intr-un lichid ( presiunea de vapori a lichidului este neglijata) este
direct proportionala cu fractia sa molara:
p
a
= Kx
a
Aceasta lege este valabila pentru gaze greu solubile CO, N
2
si nu pentru gaze care dau si reactii cu solventul cum ar fi hidracizii in apa.
H
2
S gaz incolor cu miros specific de oua clocite, putin mai greu decat aerul solubil in apa ~ 290 cc / 100 ml apa la 20
0
C, foarte toxic.
Punctele de fierbere a hidracizilor puri si legaturile de hidrogen



Aciditatea
Taria acida este foarte slaba pentru HF in timp ce toti ceilalati hidracizi din serie sunt acizi tari. Faptul ca manifesta aceeasi tarie este cunoscut ca
fenomenul de nivelare a tariei acide in solutia acida, deoarece taria acida este conditionata de disocierea acidului in solvent si toti hidracizii
disociaza complet si dau aceeasi concentratie de hidroniu:
HX + H
2
O H
3
O
+
+ Cl


In schimb in solventii acizi comportarea este diferita. In acidul acetic acizii tari devin acizi slabi, foarte putin disociati
HCl + CH
3
OOH CH
3
OO
+
H
2
+ Cl


Taria acida se poate discuta si in termenii energiei libere Gibbs G = RT ln Ka unde G = H - T S, unde aciditatea mica a HF este
conditionata de energia de legatura H-F mare fata de ceilalti hidracizi in timp ce hidratarea protonului si a halogenurii gazoase are valorile:
H-Cl H Br H I
G kcal/mol - 332 - 325 - 317
Taria acida devine totusi foarte relative daca tinem cont de faptul ca in solutii 5-15 m procesul de ionizare a acidului fluorhidric este mult mai
complex si au loc reactiile:
HF + H
2
O H
3
O
+
+ F


HF + F

HF
2
-

HF + HF
2
-
H
2
F
3
-

Si astfel acidul fluorhidric devine un acid tare prin prezenta acestor anioni stabili. Ca lichid pur H-F se comporta ca un acid foarte tare 2
2 HF H
2
F
+
+ F


Fata de acceptorii puternici de anioni fluorura cum ar fi: BF
3
, SbF
5
, AsF
5
, SnF
4
cu care da urmatoarele echilibre:
SbF
5
+ 2 HF [SbF
6
]
-
+ H
2
F
+

In timp ce cu acidul azotic se comporta ca o baza: HNO
3
+ HF H
2
NO
3
+
+ F
-


Amestecuri azeotrope unele solutii prezinta la o anumita compozitie p.t. mai mari sau mai mici decat componentii puri. Compozitia
amestecului cu aceasta proprietate se numeste amestec azeotrop.
Ex; C
2
H
5
OH H
2
O amestecul azeotrop 95% EtOH
p.t. 78.30
0
C 100
0
C 78.15
0
C
Hidracizii formeaza amestecuri azeptrope cu apa si pot fi eliberati din aceste solutii prin incalzire sau prin picurarea de acid sulfuric.

HALOGENURILE
Compusi binari ai metalelor si ai nemetalelor.
Halogenurile metalice au character de sare si au formula generala MXn,

Floruri importamte
Calcium fluoride (CaF
2
) is a colourless solid that is relatively insoluble in water and dilute acids and bases. It is used to produce steel, glass
and enamel (because it lowers the melting temperature), hydrofluoric acid and anhydrous hydrogen fluoride (as raw material), and aluminium (as
electrolyte).
Sodium fluoride (NaF) is a colourless to white solid that is moderately soluble in water. It is used in the fluoridation of drinking water and in
the manufacture of dental preparations such as toothpaste. It is also used in the production of steel and aluminium (to lower the melting
temperature), glass and enamel, or as an insecticide and a preservative (for glues and wood).
Sulfur hexafluoride (SF
6
) is a colourless, odourless, inert gas that is slightly soluble in water and readily soluble in ethanol and bases. It is
used extensively in various electronic components and in the production of magnesium and aluminium.
Silicofluorides such as fluorosilicic acid (H
2
SiF
6
) and sodium hexafluorosilicate (Na
2
SiF
6
) are also used for the fluoridation of drinking water
supplies

Cloruri importante
Magnesium chloride serves as precursor to other magnesium compounds, for example by precipitation:
MgCl
2
(aq) + Ca(OH)
2
(aq) Mg(OH)
2
(s) + CaCl
2
(aq)
It can be electrolysed to give magnesium metal:
[5]

MgCl
2
(l) Mg(l) + Cl
2
(g)
This process is practiced on a substantial scale.
Magnesium chloride is used for a variety of other applications besides the production of magnesium: the manufacture of textiles, paper,
fireproofing agents, cements and refrigeration brine,
[5]
and dust and erosion control. Mixed with hydrated magnesium oxide, magnesium chloride
forms a hard material called Sorel cement.
Magnesium ion Mg
2+
(usually added as the chloride) is an important component in the polymerase chain reaction, a procedure used to amplify
DNA fragments. It is generally used in experimental biology whenever RNA and DNA and their enzymes are to function in vitro, since Mg
2+
is
a necessary associate ion for nucleotides in biology, such as ATP.
Magnesium chloride is also used in several medical and topical (skin related) applications. It has been used in pills as supplemental sources of
magnesium, where it serves as a soluble compound which is not as laxitive as magnesium sulfate, and more bioavailable than magnesium
hydroxide and magnesium oxide, since it does not require stomach acid to produce soluble Mg
2+
ion. It can also be used as an effective
anaesthetic for cephalopods, some species of crustaceans,
[6]
and several species of bivalve, including oysters
[7]

Culinary use
Magnesium chloride is an important coagulant (E511
[8][clarification needed]
) used in the preparation of tofu from soy milk. In Japan it is sold as nigari
(, derived from the Japanese word for "bitter"), a white powder produced from seawater after the sodium chloride has been removed, and
the water evaporated. In China it is called lushui (). Nigari or lushui consists mostly of magnesium chloride, with some magnesium sulfate
and other trace elements. It is also an ingredient in baby formula milk. There is also 40 mg magnesium chloride in the bottled drink Vitamin
Water, in the flavour 'Multi-v', lemonade [a-zinc].
Use as an anti-icer
A number of state highway departments throughout the United States have decreased the use of rock salt and sand on roadways and have
increased the use of solutions of magnesium chloride (often called "liquid magnesium chloride") as a de-icer or anti-icer. Magnesium chloride is
much less toxic to plant life surrounding highways and airports, and is less corrosive to concrete and steel (and other iron alloys) than sodium
chloride. The liquid magnesium chloride is sprayed on dry pavement (tarmac) prior to precipitation or wet pavement prior to freezing
temperatures in the winter months to prevent snow and ice from adhering and bonding to the roadway. The application of anti-icers is utilized in
an effort to improve highway safety. Magnesium chloride is also sold in crystal form for household and business use to de-ice sidewalks and
driveways. In these applications, the compound is applied after precipitation has fallen or ice has formed, instead of previously.
The use of this compound seems to show an improvement in driving conditions during and after freezing precipitation, but it can damage electric
utilities. This occurs in two ways: contamination of insulators, causing tracking and arcing across them, and corrosion of steel and aluminium
poles and pole hardware.
Use in dust and erosion control
Road departments and private industry may apply liquid or powdered magnesium chloride to control dust and erosion on unimproved (dirt or
gravel) roads and dusty job sites such as quarries. Its hygroscopy makes it absorb moisture from the air, controlling the number of small particles
which become airborne. Magnesium Chloride is acidic due to the hydrochloric compound for the amplification of electrified hydrogen atoms.
Owners of indoor arenas (e.g. for horse riding) may apply magnesium chloride to sand or other floor materials to control dust.
Use in hydrogen storage
Magnesium chloride has shown promise as a storage material for hydrogen. Ammonia, which is rich in hydrogen atoms, is used as an
intermediate storage material. Ammonia can be effectively adsorbed onto solid magnesium chloride, forming Mg(NH
3
)
6
Cl
2
. Ammonia is
released by mild heat, and is then passed through a catalyst to give hydrogen gas.
Medical use
MgCl
2
was one of the earlier antiseptics, first used for that purpose by Dr. Pierre Delbet in 1915. One veterinary study in 1989 indicated some
effectiveness against tumors when used as a feed additive.
[9]

Marine aquarium use
Magnesium in natural seawater values are between (1250 mg/L-1350 mg/L). Magnesium helps to stabilize the correct combination of calcium,
alkalinity and ph values. Severely low values of magnesium (900 mg/L or below) can cause low pH values and an inability to maintain proper
alkalinity and calcium values. If magnesium becomes too low, coral growth will stop and followed by a decline in coral health. Carbonates and
calcium are essential for all growth of corals, coralline algae, clams and invertebrates. Maintaining the correct magnesium values is very
important and is indirectly responsible for coral and coralline algae growth by making it possible to maintain correct calcium, alkalinity and pH
values. Magnesium can be depleted by mangrove plants and the use of excessive Kalkwasser or by going beyond natural calcium, alkalinity and
pH values.
[10]



1
Nemetale proprietati fizice


Grupa VII/17


- constante fizice , mirosuri intepatoare si foarte toxice







Raza atomica electronegativitatea afinitatea pentru electroni


halogenul F
2
Cl
2
Br
2
I
2

culoarea Gaz slab galbui Gaz galben verzui Lichid brun roscat / vapori bruni roscati Solid negru cenusiu, lucios, vapori violeti
Element Raza atomica (A) Raza ionica (A) Energia de ionizare (kJ mol
-1
) Electron affinity Electro negativity
F 0.72 1.86 1681 332.6 4.0
Cl 0.99 1.81 1255 348.5 3.0
Br 1.14 1.95 1142 324.7 2.8
I 1.33 2.16 1007 295.5 2.5
2


Molecule structura model d(XX) / A
0
F
2
1,49 [He] 2s
2
, 2p
5

Cl
2
1,98 [Ne] 3s
2
, 3p
5

Br
2
2,27 [Ar] 3d
10
, 4s
2
, 4p
5

I
2
2,72 [Kr] 4d
10
, 5s
2
, 5p
5



Variatia nergiei de legatura intre moleculele de halogeni
3


Solubilitatea halogenilor

solventi F
2
Cl
2
Br
2
I
2

X2 + HOH HX + HOX
Solventi
polari
Protici Apa H-OH, - Galbuie Cl
2
.8H
2
O Brun NH
4
+
, Cl
-
, Br
-
/Br
2
.7H
2
O Brun KI
acidul acetic CH
3
CO-OH,
metanol CH
3
-OH,
etanol CH
3
CH
2
-OH,
n-propanol CH
3
CH
2
CH
2
-OH,
n-butanol CH
3
CH
2
CH
2
CH
2
-OH

aprotici Cu
oxigen
acetona CH
3
)
2
C=O ,
acetate de etil CH
3
COOCH
2
CH
3
,
dimetil sulfoxid (CH
3
)
2
SO ,
dimetilformamida HCON(CH
3
)
2

S
+
Br
-
/ S
-
Br
+
S
+
I
-
/ S
-
I
+

Fara
oxigen
Acetonitril CH
3
CN, Br
+
- Br
-
I
+
- I
-

Chloroform CHCl
3

Solventi
nepolari
Fara
oxigen
benzene C
6
H
6
,
hexane CH
3
(CH
2
)
4
CH
3
,
carbon tetrachloride CCl
4
,
methylene chloride CH
2
Cl
2

- Br
2
liber I
2
liber
Cu oxigen diethyl ether CH
3
CH
2
OCH
2
CH
3
1.4 dioxan

O

(CH
2
)
4
O


Br
+
- Br
-
usor polarizat I
+
- I
-

4
Explicatia culorii




1,4 dioxan si bromul

Transferul de sarcina este raspunzator de culoare un electron de al solventului trece pe un OMAL al moleculei de halogen










5

Structura cristalina a iodului




Amidon iod in amidon





6
Grupa VI / 16

Alotropia = proprietatea unui element de a exista in doua sau mai multe forme distincte care sunt chimic identice dar prezinta proprietati fizice distincte
dat fiind aranjarea diferita a atomilor in reteaua cristalina.
Enatiotropia = proprietatea unui element de a prezenta doua forme alotrope care pot trece reversibil una in alta finnd stabile la temperaturi diferite








proprietatea Oxigenul Sulful Seleniu Teluriu Poloniu
Raza atomica (A
o
) 0.73 1.09 1.16 1.35 -
Raza ionica (A
o
) O
2-
, S
2-
, Se
2-
, Te
2-
, 1.40 1.85 1.98 2.21 -
Energia de ionizare (kJ mol
-1
) 1314 1000 941 869 -
Electronegativitate 3.5 2.5 2.4 2.1 2.0
Afinitatea pentru electroni (k.J mol
-1
) 141.4 208.8 195.5 190.0 -
P.T. (K) 54 392 490 723 527
P.F. (K) 90 718 958 1263 1235
7





Caracteri
stice
fizice in
conditii
normale
Gaz este un gaz cu
molecula diatomica care
condenseaza la
182.95 C, fara culoare,
gust si miros.

Solid inodor, fara gust, galben, cu retea
cristalina in care intra unitati de S
8.

-Cristale metalice lucioase
negre-gri,
- cristale nemetalice
rosietice
Se dizolva in alcalii si acid
azotic concentrate.
-telurul amorf precipitat din acidul
telluric Te(OH)
6

- telurul metallic alb argintiu are
proprietati semiconductoare care cresc
prin expunerea la lumina
fotoconductor

-element radioactive,
prezinta doua forme
allotrope Po cubic

Po romboedric
Forme
alotrope
ozon O
3
blue

tetraoxigen O
4
-
Enantiotropia



negru, gri rosie
seleniu
Are 8 izotopi naturali dintre care
patru
122
Te,
124
Te,
125
Te ,
126
Te,
stabili si ceilalti radioactivi
120
Te,
123
Te,
128
Te and
130
Te. Izotopii
stabili reprezinta numai 33.2 %
deoarece restul este asigurat de
izotopii radioactivi care desi
instabili au timp de injumatatire cel
mare de 10
13
-2.2 10
24
ani dintre
tori izotopii.


8







octaoxigen O
8
- red




9

GRUPA V
GRUPA IV
Si
F
2
SiF
4
O
2
SiO
2
N
2
1300

0
C
Si
3
N
4
aliaj e
anticorozive
(Ti, V, Nb, Ta) MSi, MSi
2
, M
2
Si
H
2
O
SiO
2

+
H
2
NaOH
Na
4
SiO
4

+
H
2
oxizi metalici
MgO, BaO
SiO
2

+
(Mg, Ba)
saruri
amestec de acizi
Si
+
Na
2
CO
3
= Na
4
SiO
4

+
CO
Si
+

2
HNO
3

+

6
HF = H
2
[SiF
6
]
, S
C
(SiO
2

+
C)
SiC carborund
durit ate asemanatoare cu diamantul
metale
Si
+
Mg Mg
2
Si
+
HCl
SiH
4
seria silanilor
H
2
SiO aldehida silicoformica
-
prin polimerizare da (H
2
SiO)n
-
siloxanii
H
4
Si
2
O
4
acidul silicoxalic HOOSi _ Si OOH si derivatii silanolii prin (OH)
3
Si _ Si(OH)
3
SiH
3
OH silanol cu derivatii siloxani care sunt eteri H
3
Si _ O _ SiH
3
H_Si Si _OH da polimeri ramificati de tip siloxeni

10
- siliconii sunt derivati ai (CH
3
)
2
SiCl
2
( Si + 2 CH
3
Cl ) care prin hidroliza dau unitatea structurala a rasinilor de tip siliconi (CH
3
)
2
Si (OH)
2



HIDROGENUL
BORUL
1
HIDROGENUL
Hidrogenul cel mai abundent element 75 % in univers, spatiul interstellar ca plasma , prezenta lui in sfera gravitationala este foarte rara.
Galaxia cu regiunea hidrogenului ionizat

Istoric
- Paracelsus, 14931541) via the mixing of metals with strong acids.

- 1671, Robert Boyle rediscovered and described the reaction between iron filings and dilute acids,
- In 1766, Henry Cavendish was the first to recognize hydrogen gas as a discrete substance, by identifying the gas from a metal-acid reaction as
"flammable air" and further finding in 1781 that the gas produces water when burned.
- In 1783, Antoine Lavoisier gave the element the name hydrogen (from the Greek hydro meaning water and genes meaning
creator)
[58]
when he and Laplace reproduced Cavendish's finding that water is produced when hydrogen is burned.
[57]

- Hydrogen was liquefied for the first time by James Dewar in 1898 by using regenerative cooling and his invention, the vacuum flask.
[57]

- Deuterium was discovered in December 1931 by Harold Urey,
- tritium was prepared in 1934 by Ernest Rutherford, Mark Oliphant, and Paul Harteck.
[56]
Heavy water, which consists of deuterium in the place
of regular hydrogen, was discovered by Urey's group in 1932.
[57]

- Franois Isaac de Rivaz built the first internal combustion engine powered by a mixture of hydrogen and oxygen in 1806. Edward Daniel
Clarke invented the hydrogen gas blowpipe in 1819.
2
- The Dbereiner's lamp and limelight were invented in 1823.
[57]

The first hydrogen-filled balloon was invented by Jacques Charles in 1783.
-
German count Ferdinand von Zeppelin promoted the idea of rigid airships lifted by hydrogen that later were called Zeppelins; the first of which
had its maiden flight in 1900.
-
Regularly scheduled flights started in 1910 and by the outbreak of World War I in August 1914, they had carried 35,000 passengers without a
serious incident. Hydrogen-lifted airships were used as observation platforms and bombers during the war.

Producerea
Laboratory
In the laboratory, H
2
is usually prepared by the reaction of acids on metals such as zinc with Kipp's apparatus.
Zn + 2 H
+
Zn
2+
+ H
2

Aluminium can also produce H
2
upon treatment with bases:
2 Al + 6 H
2
O + 2 OH

2 Al(OH)4 + 3 H
2

The electrolysis of water is a simple method of producing hydrogen. A low voltage current is run through the water, and gaseous oxygen forms
at the anode while gaseous hydrogen forms at the cathode. Typically the cathode is made from platinum or another inert metal when producing
hydrogen for storage. If, however, the gas is to be burnt on site, oxygen is desirable to assist the combustion, and so both electrodes would be
made from inert metals. (Iron, for instance, would oxidize, and thus decrease the amount of oxygen given off.) The theoretical maximum
efficiency (electricity used vs. energetic value of hydrogen produced) is between 8094%.
[71]

2H
2
O(aq) 2H
2
(g) + O
2
(g)
In 2007, it was discovered that an alloy of aluminium and gallium in pellet form added to water could be used to generate hydrogen. The process
also creates alumina, but the expensive gallium, which prevents the formation of an oxide skin on the pellets, can be re-used. This has important
potential implications for a hydrogen economy, since hydrogen can be produced on-site and does not need to be transported.
[72]

3
Industrial
1. Hydrogen can be prepared in several different ways, but economically the most important processes involve removal of hydrogen from
hydrocarbons. Commercial bulk hydrogen is usually produced by the steam reforming of natural gas.
[73]
At high temperatures (10001400 K,
C;7001100 C or 1,3002,000 F), steam (water vapor) reacts with methane to yield carbon monoxide and H
2
.
CH
4
+ H
2
O CO + 3 H
2

This reaction is favored at low pressures but is nonetheless conducted at high pressures (2.0 MPa, 20 atm or 600 inHg) since high pressure H
2
is
the most marketable product and Pressure Swing Adsorption (PSA) purification systems work better at higher pressures. The product mixture is
known as "synthesis gas" because it is often used directly for the production of methanol and related compounds. Hydrocarbons other than
methane can be used to produce synthesis gas with varying product ratios. One of the many complications to this highly optimized technology is
the formation of coke or carbon:
CH
4
C + 2 H
2

Consequently, steam reforming typically employs an excess of H
2
O. Additional hydrogen can be recovered from the steam by use of carbon
monoxide through the water gas shift reaction, especially with an iron oxide catalyst. This reaction is also a common industrial source of carbon
dioxide:
[73]

CO + H
2
O CO
2
+ H
2

2. Other important methods for H
2
production include partial oxidation of hydrocarbons:
[74]

2 CH
4
+ O
2
2 CO + 4 H
2

and the coal reaction, which can serve as a prelude to the shift reaction above:
[73]

C + H
2
O CO + H
2

4
3. Hydrogen is sometimes produced and consumed in the same industrial process, without being separated. In the Haber process for the
production of ammonia, hydrogen is generated from natural gas.
[75]
Electrolysis of brine to yield chlorine also produces hydrogen as a co-
product.
[76]
Proprietati fizice

Color colorless , Phase gas , Density (0 C, 101.325 kPa) 0.08988 g/L , Liquid density at m.p. 0.07 (0.0763 solid)
[2]
gcm
3
, Melting point
14.01 K, -259.14 C, Boiling point 20.28 K, -252.87 C, -423.17 F Triple point 13.8033 K (-259C), 7.042 kPa , Critical point 32.97 K,
1.293 MPa, Heat of fusion (H
2
) 0.117 kJmol
1
, Heat of vaporization (H
2
) 0.904 kJmol
1
, Specific heat capacity (25 C) (H
2
) 28.836
Jmol
1
K
1


1
H protonul 99.98%.

2
H, deuterium utilizat in
1
H-NMR spectroscopy, neutron moderator .

3
H tritium este radioactiv, se descompune in Helium-3 si beta decay cu timp de injumatatire de 12.32 years. Catitati mici se gasesc in radiatia
cosmica, se foloseste ca radioizotop la marcare.
Protonul prezinta doi izomeri de spin
In the orthohydrogen form, the spins of the two protons are parallel and form a triplet state with a molecular spin quantum number of 1 (+);
in the parahydrogen form the spins are antiparallel and form a singlet with a molecular spin quantum number of 0 (-).
5
At standard temperature and pressure, hydrogen gas contains about 25% of the para form and 75% of the ortho form, also known as the "normal
form".
[20]
The equilibrium ratio of orthohydrogen to parahydrogen depends on temperature, but since the ortho form is an excited state and has a
higher energy than the para form, it is unstable and cannot be purified. At very low temperatures, the equilibrium state is composed almost
exclusively of the para form.
Combustion
Hydrogen formeaza un amestec exploziv cu aerul in proportie de 4-74% (continut procentual in volume de hydrogen in aer) si cu clorul in
proportie de 5-95%. Amestecul detoneaza imidiat la incalzire 500 C, lovire sau lumina UV.
2 H
2
(g) + O
2
(g) 2 H
2
O(l) + 572 kJ (286 kJ/mol)
[note 1]

H
2
reacts with every oxidizing element. Hydrogen can react spontaneously and violently at room temperature with chlorine and fluorine to form
the corresponding hydrogen halides, hydrogen chloride and hydrogen fluoride, which are also potentially dangerous acids.
[15]

Flacara de hydrogen pur in oxigen emite lumina UV invizibilaThe detection of a burning hydrogen leak may require a flame detector; such leaks
can be very dangerous. The destruction of the Hindenburg airship was an infamous example of hydrogen combustion; the cause is debated, but
the visible flames were the result of combustible materials in the ship's skin.
[13]
Because hydrogen is buoyant in air, hydrogen flames tend to
ascend rapidly and cause less damage than hydrocarbon fires. Two-thirds of the Hindenburg passengers survived the fire, and many deaths were
instead the result of falls or burning diesel fuel.
[14]



6
The Space Shuttle Main Engine burns hydrogen with oxygen, producing a nearly-invisible flame at full thrust.

Aplicatii
H
2
in industria chimica si petroliera.
ammonia. \
hydrodealkylation, hydrodesulfurization, and hydrocracking.
Agent de hidrogenare in uleiuri
hydrochloric acid.
reducing agent of metallic ores.
[79]

Hydrogen is highly soluble in many rare earth and transition metals
[80]
and is soluble in both nanocrystalline and amorphous metals.
[81]
Hydrogen
solubility in metals is influenced by local distortions or impurities in the crystal lattice.
[82]
These properties may be useful when hydrogen is
purified by passage through hot palladium disks, but the gas serves as a metallurgical problem as hydrogen solubility contributes in an unwanted
way to embrittle many metals,
[7]
complicating the design of pipelines and storage tanks.
[8]

Apart from its use as a reactant, H
2
has wide applications in physics and engineering. It is used as a shielding gas in welding methods such as
atomic hydrogen welding.
[83][84]
H
2
is used as the rotor coolant in electrical generators at power stations, because it has the highest thermal
conductivity of any gas. Liquid H
2
is used in cryogenic research, including superconductivity studies.
[85]
Since H
2
is lighter than air, having a
little more than
1

15
of the density of air, it was once widely used as a lifting gas in balloons and airships.
[86]

In more recent applications, hydrogen is used pure or mixed with nitrogen (sometimes called forming gas) as a tracer gas for minute leak
detection. Applications can be found in the automotive, chemical, power generation, aerospace, and telecommunications industries.
[87]
Hydrogen
is an authorized food additive (E 949) that allows food package leak testing among other anti-oxidizing properties.
[88]

Energy carrier
See also: Hydrogen economy and Hydrogen infrastructure
Hydrogen is not an energy resource,
[93]
except in the hypothetical context of commercial nuclear fusion power plants using deuterium or tritium,
a technology presently far from development.
[94]
The Sun's energy comes from nuclear fusion of hydrogen, but this process is difficult to achieve
controllably on Earth.
[95]
Elemental hydrogen from solar, biological, or electrical sources require more energy to make it than is obtained by
7
burning it, so in these cases hydrogen functions as an energy carrier, like a battery. Hydrogen may be obtained from fossil sources (such as
methane), but these sources are unsustainable.
[93]

The energy density per unit volume of both liquid hydrogen and compressed hydrogen gas at any practicable pressure is significantly less than
that of traditional fuel sources, although the energy density per unit fuel mass is higher.
[93]
Nevertheless, elemental hydrogen has been widely
discussed in the context of energy, as a possible future carrier of energy on an economy-wide scale.
[96]
For example, CO
2
sequestration followed
by carbon capture and storage could be conducted at the point of H
2
production from fossil fuels.
[97]
Hydrogen used in transportation would burn
relatively cleanly, with some NOx emissions,
[98]
but without carbon emissions.
[97]
However, the infrastructure costs associated with full
conversion to a hydrogen economy would be substantial.
[99]

Hydrogen storage technologies can be divided into physical storage, where hydrogen molecules are stored
(including pure hydrogen storage via compression and liquefication), and chemical storage, where hydrides
are stored.
Chemical storage

Metal hydride hydrogen storage
Metal hydrides, like LiH, NaAlH
4
, LiAlH
4
, LaNi
5
H
6
and TiFeH
2
, with varying degrees of efficiency, can be used as a storage medium for
hydrogen, often reversibly
[5]
. Some are easy-to-fuel liquids at ambient temperature and pressure, others are solids which could be turned into
pellets. These materials have good energy density by volume, although their energy density by weight is often worse than the leading
hydrocarbon fuels. Any hydride will need to be recharged with hydrogen
[6]
. Hydrogen stations are becoming available in some parts of the
world. Home hydrogen generators can also be used to charge the vehicle's hydrogen tanks. The generator creates hydrogen from a water supply
and an energy source, such as a solar panel, wind turbine, or electrical outlet.
8

Most metal hydrides bind with hydrogen very strongly. As a result high temperatures around 120 C (248 F) - 200 C (392 F) are required to
release their hydrogen content. This energy cost can be reduced by using alloys which consists of a strong hydride former and a weak one such
as in LiNH
2
, NaBH
4
and LiBH
4
. These are able to form weaker bonds, thereby requiring less input to release stored hydrogen. However if the
interaction is too weak, the pressure needed for rehydriding is high, thereby eliminating any energy savings. The target for onboard hydrogen
fuel systems is roughly <100C for release and <700 bar for recharge (20-60 kJ/mol H2 )
[7][8]
.
In addition to this requirement, FreedomCAR and Vehicle Technologies (FCVT)
[9]
has established a goal of 9 wt. % hydrogen for 2015 onboard
storage systems. Currently the only hydrides which are capable of achieving this goal are limited to lithium, boron and aluminum based
compounds; at least one of the first-row elements or Al must be added. Research is being done to determine new compounds which can be used
to meet these requirements.
9
Proposed hydrides for use in a hydrogen economy include simple hydrides of magnesium
[10]
or transition metals and complex metal hydrides,
typically containing sodium, lithium, or calcium and aluminium or boron. Hydrides chosen for storage applications provide low reactivity (high
safety) and high hydrogen storage densities. Leading candidates are Lithium hydride, sodium borohydride, lithium aluminium hydride and
ammonia borane.
New Scientist
[11]
stated that Arizona State University is investigating using a borohydride solution to store hydrogen, which is released when the
solution flows over a catalyst made of ruthenium.
Carbohydrates
Carbohydrates (Polymeric C
6
H
10
O
5
) releases H
2
in an bioreformer mediated by the enzyme cocktail -- cell-free synthetic pathway
biotransformation. Carbohydrate provides high hydrogen storage densities as a liquid with mild pressurization and cryogenic constraints: It can
also be stored as a solid power. Carbohydrate is the most abundant renewable bioresource in the world.
In May 2007 biochemical engineers from the Virginia Tech University and biologists and chemists from the Oak Ridge National Laboratory
announced a method of producing high-yield pure hydrogen from starch and water
[12]
. In 2009, they demonstrated to produce nearly 12 moles of
hydrogen per glucose unit from cellulosic materials and water
[13]
. Thanks to complete conversion and modest reaction conditions, they propose
to use carbohydrate as a high energy density hydrogen carrier with a density of 14.8 wt %.
[14]

Synthesized hydrocarbons
An alternative to hydrides is to use regular hydrocarbon fuels as the hydrogen carrier. Then a small hydrogen reformer would extract the
hydrogen as needed by the fuel cell. However, these reformers are slow to react to changes in demand and add a large incremental cost to the
vehicle powertrain.
Direct methanol fuel cells do not require a reformer, but provide a lower energy density compared to conventional fuel cells, although this could
be counter balanced with the much better energy densities of ethanol and methanol over hydrogen. Alcohol fuel is a renewable resource.
Solid-oxide fuel cells can operate on light hydrocarbons such as propane and methane without a reformer, or can run on higher hydrocarbons
with only partial reforming, but the high temperature and slow startup time of these fuel cells are problematic for automotive applications.
Ammonia
10
Further information: Ammonia production
Ammonia (NH
3
) releases H
2
in an appropriate catalytic reformer. Ammonia provides high hydrogen storage densities as a liquid with mild
pressurization and cryogenic constraints: It can also be stored as a liquid at room temperature and pressure when mixed with water. Ammonia is
the second most commonly produced chemical in the world and a large infrastructure for making, transporting, and distributing ammonia exists.
Ammonia can be reformed to produce hydrogen with no harmful waste, or can mix with existing fuels and under the right conditions burn
efficiently. Pure ammonia burns poorly at the atmospheric pressures found in natural gas fired water heaters and stoves. Under compression in
an automobile engine it is a suitable fuel for slightly modified gasoline engines. Ammonia is a toxic gas at normal temperature and pressure and
has a potent odor
[15]
.
In September 2005 chemists from the Technical University of Denmark announced a method of storing hydrogen in the form of ammonia
saturated into a salt tablet. They claim it will be an inexpensive and safe storage method.
[16]

Amine borane complexes
Prior to 1980, several compounds were investigated for hydrogen storage including complex borohydrides, or aluminohydrides, and ammonium
salts. These hydrides have an upper theoretical hydrogen yield limited to about 8.5% by weight. Amongst the compounds that contain only B, N,
and H (both positive and negative ions), representative examples include: amine boranes, boron hydride ammoniates, hydrazine-borane
complexes, and ammonium octahydrotriborates or tetrahydroborates. Of these, amine boranes (and especially ammonia borane) have been
extensively investigated as hydrogen carriers. During 1970's and 80's, the U.S. Army and Navy funded efforts aimed at developing
hydrogen/deuterium gas-generating compounds for use in the HF/DF and HCl chemical lasers, and gas dynamic lasers. Earlier hydrogen gas-
generating formulations used amine boranes and their derivatives. Ignition of the amine borane(s) forms boron nitride (BN) and hydrogen gas. In
addition to ammonia borane (H
3
BNH
3
), other gas-generators include diborane diammoniate, H
2
B(NH
3
)
2
BH
4
.
Formic acid
In 2006 researchers of EPFL, Switzerland, reported the use of formic acid as a hydrogen storage material
[17]
. Carbon monoxide free hydrogen
has been generated in a very wide pressure range (1-600 bar). A homogeneous catalytic system based on water soluble ruthenium catalysts
selectively decompose HCOOH into H
2
and CO
2
in aqueous solution
[18]
. This catalytic system overcomes the limitations of other catalysts (e.g.
poor stability, limited catalytic lifetimes, formation of CO) for the decomposition of formic acid making it a viable hydrogen storage material
[19]
.
And the co-product of this decomposition, carbon dioxide, can be used as hydrogen vector by hydrogenating it back to formic acid in a second
step. The catalytic hydrogenation of CO
2
has long been studied and efficient procedures have been developed
[20][21]
. Formic acid contains 53 g L
-
11
1
hydrogen at room temperature and atmospheric pressure. By weight, pure formic acid stores 4.3 wt% hydrogen. Pure formic acid is a liquid
with a flash point 69 C (cf. gasoline -40 C, ethanol 13 C). 85% formic acid is not inflammable.
Imidazolium ionic liquids
In 2007 Dupont and others reported hydrogen-storage materials based on imidazolium ionic liquids. Simple alkyl(aryl)-3-methylimidazolium N-
bis(trifluoromethanesulfonyl)imidate salts that possess very low vapour pressure, high density, and thermal stability and are not inflammable can
add reversibly 6-12 hydrogen atoms in the presence of classical Pd/C or Ir0 nanoparticle catalysts and can be used as alternative materials for on-
board hydrogen-storage devices. These salts can hold up to 30 g L
-1
of hydrogen at atmospheric pressure.
[22]

Phosphonium borate
In 2006 researchers of University of Windsor reported on reversible hydrogen storage in a non-metal phosphonium borate frustrated Lewis
pair
[23][24][25]
:

The phosphino-borane on the left accepts one equivalent of hydrogen at one atmosphere and 25C and expels it again by heating to 100C. The
storage capacity is 0.25 wt% still rather below the 6 to 9 wt% required for practical use.
Carbonite substances
Research has proven that graphene can store hydrogen efficiently. After taking up hydrogen, the substance becomes graphane. After tests,
conducted by dr Andr Geim at the University of Manchester, it was shown that not only can graphene store hydrogen easily, it can also release
the hydrogen again, after heating to 450C.
[26][27]

12
Physical storage
Carbon nanotubes
Hydrogen carriers based on nanostructured carbon (such as carbon buckyballs and nanotubes) have been proposed. Despite initial claims of
greater than 50 wt% hydrogen storage, it has generally come to be accepted that less than 1 wt% is practical.
[28]

Metal-organic frameworks
Metal-organic frameworks represent another class of synthetic porous materials that store hydrogen. In 2006, chemists at UCLA and the
University of Michigan have achieved hydrogen storage concentrations of up to 7.5% weight in MOF-74
[29]
. However, the storage was achieved
at the low temperature of 77 K.
[30]
. In 2009 researchers of the University of Nottingham reached 10 wt% at 77 bar (1,117 psi) and 77 K with
MOF NOTT-112
[31]
.
Clathrate hydrates
H
2
caged in a clathrate hydrate was first reported in 2002, but requires very high pressures to be stable. In 2004, researchers from Delft
University of Technology and Colorado School of Mines showed solid H
2
-containing hydrates could be formed at ambient temperature and 10s
of bar by adding small amounts of promoting substances such as THF.
[32]
These clathrates have a theoretical maximum hydrogen densities of
around 5 wt% and 40 kg/m
3
.
Doped polymers
In 2006, a team of Korean researchers led by Professor Jisoon Ihm at Department of Physics and Astronomy of Seoul National University
proposed a new material with the hydrogen storage efficiency of 7.6 percent based on first-principles electronic structure calculations for
hydrogen binding to metal-decorated polymers of many different kinds. According to these researchers, hydrogen can be stored in a solid
material at ambient temperatures and pressures by attaching a titanium atom to a polyacetylene. [5][6]
Glass Capillary Arrays
13
A team of Russian, Israeli and German scientists have collaboratively developed an innovative technology based on glass capillary arrays for the
safe infusion, storage and controlled release of hydrogen in mobile applications[7][8]. The C.En [9] technology has achieved the US Department
of Energy (DOE) 2010 targets for on-board hydrogen storage systems
[33]
.
Glass microspheres
Hollow glass microspheres (HGM) can be utilized for controlled storage and release of hydrogen.
[34][35]

Keratine
Keratine, a compound found in bird feathers, has been found to be useful to increase the interior surface (and thus the hydrogen storage capacity)
of tanks. The research stated that the use of carbonized chicken feather fibres would result in far lower manufacturing costs than other common
hydrogen tanks on the market. The research was conducted by Richard Wool and Erman Senoz.
[36]













14
HIDRURI
H
2
+ 2e

2H

; E
o
= 2.25 V

H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uuo
Uue Ubn


Hidruri
saline
Lanthanoids Actinoids
hidruri nestoichiometrice

Hidruri de
granita
Hidruri covalente
Noble
gases








15
CH
4
NH
3
H
2
O HF
obtinere 1. sinteza directa
2. deplasare din saruri
3. hidroliza
Propr.
fizice
-stare de agregare
-IR
- ABnEx simetrie
- legatura chimica, hibridizare
Solubilitate
Moment de dipole
-conductivitate electrica
-solvent
Propr.
chimice
1. character acido-bazic bazic amfoter acid
2.substituirea hidrogenului Amonoliza obtinerea ureei Hidroliza
-cloruri, sulfuri, azoturi,
carburi, fosfuri, siliciuri



SO
3
, SOCl
2

3. reactii cu elementele chimice Metale / nemetale Metale / nemetale Nu cu Ag, Au, Pt. gr. I la temp. inalte
4. reactii redox reducator
5. compusi de aditie Combinatii complexe Combinatii complexe Compusi de aditie



16
SiH
4
PH
3
H
2
S HCl
obtinere 1. sinteza directa NU P
4
+ H
2
H
2
+ S topit H
2
+ Cl
2

2. deplasare din saruri Mg
2
Si + HCl

PH
4
I + KOH ZnS, FeS, PbS Glauber
3. hidroliza fosfuri sulfuri PCl
3
, PCl
5
, SiCl
4
, SnCl
4

4. metode speciale SiCl
4
+ Li[AlH
4
]

P
4
+ KOH
P
4
+ H
2
O
H
3
PO
3
+ H
2

H
3
PO
3
H
3
PO
4
+ PH
3

S + HI, H
2
O+C,
SO
2
+ HI
Robinson
NaCl + SO
2
+ H
2
O + O
2


Propr.
fizice
-stare de agregare d=1.44, pf=-111,4 d
aer
= 1.18 d
aer
= 1.12
-IR
- ABnEx simetrie C
3v

- legatura chimica,
hibridizare, legaturi de
hidrogen
Si-H 80.5 Kcla/mol
1.55A
0

HPH = 92
0
HSH = 92 H-Cl
Solubilitate
Moment de dipole = 0.36D = 1.045D
-conductivitate
electrica

-solvent PH
3
.H
2
O H2S. 5.7 H2O
Propr.
chimice
1. character acido-bazic Saruri de fosfoniu Sulfuri
- metale, oxizi, saruri
cloruri
2.descompunere
3. substitutie SiH
4
+ Br
2
PH
3
+ X2, S, M
3. reactii redox oxidare oxidare oxidare oxidare
4. compusi de aditie



17
Hidruri importante H
2
O
Alte tipuri de hidruri importante hidruri derivate de la NH
3
, H
2
O