Elements of the Sea

Ionic equations
o If 2 solutions react to form a solid, a precipitation reaction
occurs. Eg. Ag+(aq) + No3(aq) + Na+(aq) + !r(aq) goes to
Ag!r(s) + Na+"aq# + N$3(aq)
%hen cancel spectators
Ag+(aq) + !r(aq) goes to Ag!r(s)
o Al&a's include state s'm(ols
o $nl' split into ions if aqueous and ionic
Ionic solids
o )ations and anions are held together (' strong electrostatic
attractions in a giant ionic lattice.
o Each sodium ion is surrounded ('
* chloride ions *+* coordination. It
is a simple cu(ic structure.
o Ionic solids are hard and ha,e a
high melting point due to strong
electrostatic attractions (et&een
ions.
o If ionic cr'stals contain &ater, the
&ater molecules fit into the lattice
the same &a' as regular ions. %his is called the &ater of
cr'stallisation. %hese cr'stals are said to (e h'drated.
o If these h'drated cr'stals are heated, the &ater molecules
are dri,en off and 'ou are left &ith an anh'drous solid.
Ionic su(stances in solution
o As ionic su(stances dissol,e in &ater, the ions (ecome
surrounded (' &ater molecules and the' spread throughout
the solution. %he h'drated ions are randoml' arranged and
(eha,e independentl'.
o -ater surrounds the ions in this &a' (ecause it is polar and
(ent. %he partiall' + . ions are attracted to the partiall'
negati,e ions.
o In positi,e ions, the &ater molecules surround the ion &ith
the o/'gen atoms pointing in&ards, and &ith the h'drogen
atoms pointing in&ards in negati,el' charged ions.
0ules on solu(ilit'
Soluble salts Insoluble salts
All sodium, potassium and
ammonium salts.
All car(onates are insolu(le
e/cept for sodium, potassium
and ammonium car(onates.
Nitrates are al&a's solu(le
1ost chlorides, (romides and
iodides.
Sil,er and lead chlorides,
(romides and iodides.
1ost sulphates. )alcium, strontium and (arium
sulphate.
)harges on ions
Positive ions (cations) Negative ions (anions)
.'drogen .+ )hloride )l
Sodium Na+ !romide !r
Sil,er Ag+ 2luoride 2
3otassium 4+ Iodide I
5ithium 5i+ .'drogencar(onate .)$3
Ammonium N.6+ .'dro/ide $.
!arium !a2+ Nitrate N$3
)alcium )a2+ $/ide $2
)opper(II) )u2+ Sulphide S2
7inc 7n2+ Sulphate S$62
1agnesium 1g2+ )ar(onate )$32
5ead 3(2+
Iron(II) 2e2+
Iron(III) 2e3+
Aluminium Al3+
Atoms and ions
2irst ionisation enthalp'
o %he energ' needed to remo,e one electron from e,er' atom
in a mole of gaseous atoms.
o $ne mole of gaseous ions &ith one positi,e charge is
formed.
8(g) goes to 8+(g) + e
o 9nits are :;mol< and 2IE is al&a's positi,e as energ' must
(e put in to remo,e the electron as it is attracted to the
positi,e nucleus.
o %he pea:s are elements
in group # (no(le gases).
It is difficult to remo,e an
electron from these atoms
(ecause the' ha,e full
outer shells and are
unreacti,e.
o %he troughs are elements
in group <. %hese onl'
ha,e < outer shell
electron so are eas' to ionise and are ,er' reacti,e.
o It (ecomes harder to remo,e an electron across the period
( as atomic num(er increases) due to the increasing nuclear
charge.
o It (ecomes easier to remo,e an electron do&n the group as
the electron is further from the nucleus and more shielded ('
the inner shells of electrons.
o It (ecomes harder to remo,e each successi,e electron
(ecause once an electron is remo,ed from the atom, the
atom (ecomes positi,el' charged so the electrons left on
(the ones 'ou are tr'ing to remo,e) are ,er' strongl'
attracted to the atom.
o %here is a (ig =ump in IE &hen an electron is remo,ed from a
full outer shell eg. Aluminium has 3 electrons in its outer shell
so the 6
th
IE is much (igger than the 3
rd
(ecause an electron
is (eing remo,ed from a full shell.
First IE: X(g) goes to X+(g) + e-
Second IE: X+(g) goes to X2+(g) + e-
Third IE: X2+(g) goes to X+(g) + e-
Fourth IE: X+(g) goes to X!+(g) + e-
0edo/
$I50I>
$/idation is losing (electrons) reduction is gaining (electrons).
$/idation is an increase in o/idation states
0eduction is a decrease in o/idation states
$/idising agents are reduced (decrease in o/idation states)
0educing agents are o/idised (increase in o/idation states)
o ?$/'anions@ are negati,e ions that contain o/'gen and
another element. %heir names end in ?ate@ eg.sulfate. %he'
should include an o/idation state in their name.
o $/idation states should (e included in names &hen the
elements in the compound can e/ist in more than one
o/idation state. Eg. 2e$ is called iron(II) o/ide (ecause $@s
o/idation state is 2 so 2e@s o/idation state must (e +2.
o .alfequations for redo/ are as follo&s.
o If the element has (een o/idised the electron goes on
the right
o If it@s (een reduced, the electron goes on the left.
o %hin: reduced, right. !ut then s&itch it aroundA
A higher (more reacti,e) halogen o/idises a lo&er (less reacti,e)
halide.
Eg. )l2(g) + 2I(aq) goes to 2)l(aq) + I2(aq)
%his can (e split into 2 half equations+ )l2(aq) +2e goes to 2)l
(aq)reduction
2I(aq) goes to
I2(aq) + 2e o/idation
B isproportionation
In some redo/ reactions, it is the same element that is
simultaneousl' o/idised and reduced. %his is called
disproportionation. %his occurs &hen the products consist of 2
forms of the disproportionised element.
%he .alogens
3h'sical properties
Flourine+ 3ale 'ello& gas, reacts &ith &ater, solu(le in organic
sol,ents.
"hlorine+ 3ale green gas, slightl' solu(le in &ater and organic
sol,ents to gi,e a pale green solution. For#s a $hite %reci%itate
o& silver chloride $ith silver ions'
(ro#ine+ dar: red liquid, forms a (ro&n gas on &arming. Solu(le
in &ater and organic sol,ents to gi,e red(ro&n and red solutions
respecti,el'. For#s a crea# %reci%itate o& silver bro#ide $ith
silver ions'
Iodine+ Shin' (lac: solid, su(limes on &arming to gi,e a purple
,apour, (arel' solu(le in &ater to gi,e (ro&n solution, solu(le in
organic sol,ents to gi,e ,iolet solution. For#s a )ello$
%reci%itate o& silver iodide $ith silver ions'
o %he intramolecular (onds in the halogens are co,alent and
the intermolecular (onds are IBIB (onds.
o As the siCe of the molecule increases, so does the strength
of the IBIB (onds, as there are more electrons.
o %his e/plains &h' the halogens change from gas to liquid to
solid do&n the group.
o 0eacti,it' decreases do&n the group (ecause the halogens
get (igger do&n the group sot the outer electrons are less
attracted to the nucleus.
o .alogens onl' displace (o/idise) lo&er halides.
o %he general reaction of a halogen &ith sil,er ions is+
Ag+(aq) +8(aq) goes to Ag8(s)
o In redo/, halogens act as o/idising agents (decrease
o/idation states D remo,e electrons from other elements)
82 + 2e goes to 28
o )hlorine is used in &ater treatment, to ma:e (leach, .)l and
plastics. It is highl' to/ic so is transported road or rail tan:er
as a liquid.
o !romine is used to ma:e flame retardants, agricultural
fumigants and in photograph'. It@s transported in leadlined
steel tan:s in metal frames. %ransport routes a,oid
residential areas and it is often transported at night.
S3B2
Elements are split into num(er shells <6, these are split up into
su(shells, s, p, d and f.
S su(shells ha,e < or(ital and can hold 2 electrons
3 su(shells ha,e 3 or(itals and can hold * electrons
B su(shells ha,e E or(itals and can hold <# electrons.
o $r(itals fill &ith one electron in each (efore going (ac: and
putting 2 electrons in each or(ital.
o $r(itals &ith < electron in ha,e parallel spins.
o $r(itals &ith 2 electrons in ha,e opposite spins.
* *s
2 2s


!
6s is al&a's filled (efore 3d (ecause it has a lo&er energ' and the
su( shells are filled in order of increasing energ'.
Also, the d shells prefer to (e e/actl' half full or completel' full eg.
3dE or 3d<# rather than 3dF (ecause this is lo&er energ', this
therefore sometimes lea,es the 6s shell half full.
If the last electron in the element entered the s su( shell, it is said
to (e in the ?s(loc:@ of the periodic ta(le. %his is also true of the
other 3 (loc:s, p, d and f.
)hemical 1anufacturing
E/tracting !romine from sea &ater
o 3artiall' e,aporated, acidified sea &ater is &armed and
chlorine is added. It needs to (e acidified as sea &ater is
naturall' slightl' al:aline and (oth chlorine and (romine
dissol,e in al:ali.
o Steam is (lo&n through the product. !romine is gi,en off as
it is ,olatile.
o %he ,apours are condensed and as (romine is not ,er'
solu(le in &ater, t&o la'ers are formed.
o %he (romine is distilled and dried.
!atch Gs )ontinuous 3rocessH
!atch. %he starting materials are put into a ,essel and allo&ed to
react together. %he reaction is monitored and &hen complete, is
terminated. %he product is then separated from the mi/ture. %he
process is repeated (atch (' (atch.
)ontinuous. %he starting materials are fed in at one end and
&ithdra& at the other in a continuous flo&.
(atch
Ad,antages
o )ost effecti,e for small quantities
o Slo& reactions are catered for
o A range of products can (e made in the same ,essel
o A greater I con,ersion for the same amount in the same
time than &ith continuous
Bisad,antages
o )harging and empt'ing the ,essel is time consuming as is
hut do&n time.
o 5arger &or:force needed than continuous
o )ontamination is more li:el' as the same ,essel is used for
different reactions.
o E/othermic processes are difficult to control
"ontinuous
Ad,antages
o Suited to high tonnage
o >reater throughput and no need to shut do&n
o 1ore controlled as ,er' fine ad=ustment is possi(le
o )ontamination is less li:el' as is onl' used for one reaction
o )onsistent qualit' is ensured
o 1inimal &or:force and la(our needed
o 1ore easil' automated
Bisad,antages
o 1uch larger capital cost (start up costs) than (atch
o Not cost effecti,e if run (elo& capacit'
o )ontamination ris: is ,er' high if used for t&o or more
products.
>reen )hemistr' aims to reduce the use of feedstoc:s to a
minimum eg. 0ec'cle unused reactants and sol,ents and increase
atom econom'.
0educe energ' consumption eg. 9se enC'mes to reduce
temperature needed or :eep no. of steps to a minimum.
1inimise &aste D rec'cle or find &a's to ma:e use of &aste
products.
)oproducts are produced at the same time as the desired product
,ia the same reaction. As the amount of desired product increases,
so does the amount of coproducts. )oproducts can (e sold for
further profit.
!'products are the result of un&anted side reactions. %he
conditions of an' chemical process are designed to increase the
amount of desired product and decrease the amount of ('
products.
%he )hloral:ali 3rocess
%he mercur' cell
%his is (eing phased out (' 2#2# (ecause it ,er' e/pensi,e to run
and produces to/ic mercur' emissions.
%he mem(rane cell
Ad,antages+
o lo&er running costs than mercur' as less energ' used per
tonne of chlorine produced.
o 5arger capacit' for chlorine in the same space than mercur'
cell
o No need to remo,e to/ic mercur' from the products.
o 5ess en,ironmental pollution.
0eaction at the positi,e anode+ 2)l goes to )l2 +2e
0eaction at negati,e cathode+ 2.2$ +2e goes to 2$. +.2
$,erall reaction+ 2)l +2.2$ goes to )l2 +2$. +.2
C V
%he mem(rane is made from the 3%2E pol'mer and has
negati,el' charged side chains &hich the Na+ ions are attracted
to. %hese side chains repel )l and $. ions. Some &ater
molecules are attached to the sodium ions and pass through (ut
the mem(rane is impermea(le to free &ater molecules.
%he cell is designed to+
o 3re,ent chlorine from reacting &ith $.
o 1inimise )l ions diffusing into the negati,e electrode
o 1inimise the $. ions from diffusing into the positi,e
electrode
o 3re,ent h'drogen and chlorine from mi/ing (ecause the
mi/ture is e/plosi,e.
I 'ield and atom econom'
I 'ield J actual mass of product
%heoretical ma/imum mass of product /<##
%his measures the efficienc' of the reaction in terms of &aste and
ho& much of the theoretical product is actuall' produced.
I Atom econom' J 1r of useful product
1r of all reactants /<##
%his measures the efficienc' of the reactants in the process and
ho& much ends up in the products.
%itration )alculations
<dm3 J <###cm3 so to get from dm3 from cm3,
di,ide cm3 (' <###.
Steps for titrations calcs+
<. &rite out (alanced equation
2. &or: out no. of moles (nJc / ,) of one 'ou :no& c and ,
for. 0emem(er to di,ide , (' <### to change to dm3.
3. &rite do&n mole ratio, if <+< s:ip to ne/t step. If the ?n@ 'ou
=ust &or:ed out in step < is the smaller ratio then times ?n@
(' the (igger mole ratio for the ne/t purposes. If ?n@ is the
larger of the 2 then di,ide (' the larger mole ratio.
N
6. carr' out cJnK, using 'our pre,iousl' &or:ed out ?n@ ,alue
and the ?,@ gi,en in the question (remem(er to change it
into dm3 so 2E cm3 is #.#2E dm3)
Intermolecular !onds
o bond %olarit) depends on the electronegati,it' difference
(et&een the atoms
o #olecular %olarit) depends on the electronegati,it'
difference and the shape of the molecule. If molecule contain
a N$2 atom and are not s'mmetrical, the' are li:el' to
contain a 3B3B (ond.
IB IB (onds
%hese occur in all molecules and are the &ea:est t'pe of
intermolecular (onds.
!ond enthalp'
A Bipole occurs &hen a molecule has a positi,e end and a
negati,e end
-hen a molecule has a dipole &e sa' it is polarised. If a molecule
has a permanent dipole it is called a polar molecule.

%he constant mo,ement of electrons in a molecule means that at
an' one time the electron densit' ma' (e une,enl' distri(uted, this
creates an instantaneous dipole. %he polarit' of the molecule ma'
change (ecause the electron densit' is constantl' mo,ing. If other
molecules are close to the molecule &ith a dipole then electrons
get attracted to the positi,e end of the original molecule, this
induces a dipole in the ne& molecule. %he instantaneous dipole
and the induced dipole attract each other.
IBIB (onds are continuousl' forming and (rea:ing (ecause of the
constant mo,ement of electrons &ithin the molecules.
%he (igger the molecule, the more electrons it has so the greater
the attraction and the strength of the IBIB (ond so the higher the
(oiling point.
o A (igger molecule also has a larger surface area so has
more points of contact &ith neigh(ouring molecules.
o A long chain molecule has stronger IBIBs (ecause it has
more points of contact.
o A straight chain molecule has stronger IBIBs than a
(ranched chain (ecause it can line up more closel' so has
more points of contact.
3ol'(ethene) contains onl' IBIB (onds (ut is solid at room
temperature. %his is (ecause the chains are long and can pac:
close together meaning that there are man' IBIB (onds &hich
compensates for their &ea:ness.
3B3B (onds
o 1olecules &ith 3B3B (onds contain atoms &ith different
electronegati,it' ,alues.
o %he partiall' positi,e end of one molecule attracts the
partiall' negati,e end of the other.
o 3B3B (onds are stronger than IBIB (onds (ut &ea:er than
h'drogen (onds.
o 3B3B (inds hold pol'ester molecules together.
o $ccurs if the molecule is not s'mmetrical and the dipole
moments don@t cancel each other out.
o 3B3B (onds can also induce dipoles in neigh(ouring
molecules.
Electronegati,it' is the a(ilit' of an atom to attract the (onding
electron in a co,alent (ond
%he (igger the difference in electronegati,it' a molecule has, the
more ionic it is.
.alogenoal:anes
o %he homologous series of a halogenoal:ane is 08 or 0.al
&here 8 (.al) is a halogen D )l, !r or I.
o All halogenoal:anes are immisci(le &ith &ater.
o %he larger the halogen the higher the (oiling point (ecause
there &ill (e stronger IB#IB (onds (et&een the molecules.
.omol'tic 2ission
o %his forms radicals of (oth the al:ane and the halogen.
o %he condition is radiation of the right frequenc' (,isi(le or
9G) &hich is a(sor(ed (' the halogenoal:anes.
o %his :ind of reaction occurs &hen halogenoal:anes reach
the stratosphere &hich is &hat forms chlorine radicals.
o ).3)l + h, goes to ).3' +)l'
o $ne electron goes to each atom
.eterol'tic 2ission
o In .eterol'tic fission, the halogenoal:anes tend to react in a
polar sol,ent such as ethanol, or ethanol and &ater. %his is
the condition.
o No radiation is needed in this process and no radicals are
formed.
o Instead a negati,e halide ion and a positi,e car(ocation are
formed (' the complete (rea:age of the ).al (ond.
o .ere, (oth electrons go to the halogen to form a halide ion.
o %he reaction is as follo&s+
0eacti,it' trends
o Strength of ).al (ond decreases do&n the group (ecause
the siCe of the halogen atom increases.
o %herefore reacti,it' increases.
o !ond strength rather than polarit' has the greatest effect on
the reacti,it' of the halogenoal:anes.
o %his is &h' !r (onds (rea: do&n in the troposphere &hereas
)l (onds onl' (rea: do&n in the stratosphere, &rea:ing
ha,oc on the oCone la'er.
Nucleophilic su(stitution reactions
o %he general equation &here 8 is a nucleophile is as follo&s+
0.al + 8 goes to 08 + .al
o %he ).al (ond (rea:s and the halogen atom is replaced ('
the nucleophile.
o %he mechanism for the Nucleophilic su(stitution of a
halogenoal:anes is as follo&s+
o %he )I (ond is polar so the car(on atom has a partiall' +
charge and the iodine atom has a partiall' D charge.
o %he $. ion is negati,el' charged so the o/'gen is attracted
to the partiall' positi,e ) atom.
o A lone pair of electrons mo,e from the o/'gen atom to the
car(on atom as the )I (ond (rea:s.
o Iodine ions are formed, ho&e,er a free car(ocation is not
formed (ecause the $. attac:s at the same time that the )
!r (ond (rea:s.
+ nucleo%hile is a #olecule or negativel) charged ion $ith a
lone %air o& electrons that it can donate to a %ositivel)
charged ato# to &or# a covalent bond'
All halogens ha,e 3 lone pairs
%he negati,el' charged atom in the nucleophile al&a's donates
the lone pair.
-ater as a Nucleophile
o %he reaction &ith &ater as nucleophile is slo&er (ecause
&ater does not ha,e a full negati,e charge.
o %he reaction happens in t&o stepsL first the &ater attac:s the
halogenoal:ane in much the same &a' as a normal
nucleophile.
o %he second step in,ol,es the resulting positi,el' charged ion
from the first step, loses .+ to form an alcohol.
o %he o,erall equation for this reaction is+
0.al + .2$ goes to 0$. + .+ + .al
o %his reaction can also (e done in re,erse to produce
halogenoal:anes.
"onditions
0.al + $. .eat under reflu/ &ith
Na$.(aq). $ften ethanol is
added as a sol,ent
0.al + .2$ .eat under reflu/, sometimes
called h'drol'sis.
0.al + N.3 %he halogenoal:ane is heated
&ith concentrated ammonia in a
sealed tu(e.
0$. + .al In presence of a strong acid.
3reparation of halogenoal:anes
)arr'ing out the reaction
o -eigh Eg of 2meth'lpropan2ol and pour into a separating
funnel.
o >raduall' add 2#cm3 of concentrated .)l
o Sha:e the mi/ture in the separating funnel for 2# minutes
releasing the pressure from time to time.
Separating the required product from the reaction mi/ture
o Allo& the mi/ture to stand until the 2 la'ers ha,e separated.
%he alcohol ().3)3)$. &ill (e on the (ottom and
().3)3))l &ill (e on the top la'er.
o %o remo,e the e/cess acid, add sodium h'drogen car(onate
solution (ut (e careful to release the pressure as car(on
dio/ide is formed. 0un off the lo&er aqueous la'er. 0epeat
until no more gas is gi,en off.
o Add <#cm3 distilled &ater and run off aqueous la'er again.
o 0un organic ((ottom) la'er ().3)3))l into a clean conical
flas:.
o Add anh'drous sodium sulphate (a dr'ing agent) to remo,e
an' traces of &ater.
3urif'ing the product
o %he mi/ture is transferred to a flas: and then distilled.
Na#e For#ula Structure
.'dro/ide ion $.
)'anide ion )N
Ethanoate ion ).3)$$
Etho/ide ion )2.E$
-ater molecule .2$
Ammonia molecule N.3