COVENANT

UNIVERSITY
ALPHA SEMESTER TUTORIAL KIT
(VOL. 2)

PROGRAMME:CHEMISTRY
200 LEVEL
DISCLAIMER

The contents of this document are intended for practice and learning purposes at the undergraduate
level. The materials are from different sources including the internet and the contributors do not
in any way claim authorship or ownership of them. The materials are also not to be used for any
commercial purpose.

1
LIST OF COURSES

CHM211: Basic Inorganic Chemistry

CHM212: Basic Physical Chemistry
CHE212: Chemistry for Chemical Engineering I

*Not included

2
 COVENANT UNIVERSITY
CANAANLAND, KM 10, IDIROKO ROAD
P.M.B 1023, OTA, OGUN STATE, NIGERIA.
TITLE OF EXAMINATION: B.Sc EXAMINATION
COLLEGE: Science and Technology
SCHOOL: Natural and Applied Sciences
DEPARTMENT: Chemistry
SESSION: 2015/2016 SEMESTER: ALPHA
COURSE CODE: CHM 211 CREDIT UNIT: 2
COURSE TITLE: Basic Inorganic Chemistry TIME: 2 HOURS
INSTRUCTION: Attempt 3 questions in all.

1. (a) Highlight the trend of variation of ionization energy and oxidation states in the 3d, 4d and
5d transition series with reference to each of the following group VIIIB oxides: FeO4,
RuO4 and OsO4. (4½ marks)
(b) Briefly comment on the trend in bond strength of each of the following group VIB elements:
Cr, Mo and W. (2 marks)
(i) Which of these group VIB elements (Cr, Mo, W) is/are suitable for electric energy
application, why? (2 marks)
(ii) Why is the Cr /Cr couple more reducing than expected, given that the 1st , 2nd, 3rd
3+ 2+

ionization energies are 652.9, 1590.6, 2987 KJmol-1 respectively? (2 marks)

(c) MnVI undergoes disproportionation reaction in acid solution as follow:
3𝑀𝑛𝑂42− + 4𝐻 + → 𝐴 + 𝐵 + 2𝐻2 𝑂
(i) Identify the products A and B (2 marks)
(ii) Predict the crystal field splitting of ions A and B (2 marks)
(iii) If A and B are capable of forming low spin octahedral complexes, which of them
could be affected by Jahn-Teller distortion? (3 marks)
n
(d) Write the d configuration of each of the transition metal ion in the following complexes
(i) (ii) O (iii) I 2-

Cl P C
Ni
Cl Pd Co
P
C C I
C O I
O
O I
(6 marks)
2. (a) What is the effect of increase in pH on the high oxidation state of Fe in the following
half-cell reaction?
𝐹𝑒𝑂42− + 8𝐻 + + 4𝑒 − → 𝐹𝑒 2+ + 4𝐻2 𝑂 (3 𝑚𝑎𝑟𝑘𝑠)
(b) The deprotonation Fe(III) in the following reaction produces an oxygen-bridged dimer, G.
3[𝐹𝑒(𝐻2 𝑂)6 ]3+ ⇄ 𝐺 + 2𝐻 +

3
 Write the structure of G. (3 marks)
2-
(c) Complete the following reaction for the dimerization of CrO4
2𝐶𝑟𝑂42− + 𝑋 ⇌ 𝑌 + 𝐻2 𝑂 (3 𝑚𝑎𝑟𝑘𝑠)
(d) Mention two (2) examples of ‘hard’ anionic ligands and one (1) chelating ligand (3 marks)
(e) Give four (4) examples of complexes formed by each of the following 3d ions in their
higher oxidation states when reacting with the ‘hard’ anionic ligands and chelating agent
mentioned in 2(d).
(i) Ti4+ (ii) V5+ (iii) Fe3+ (iv) Co3+ (4 marks)

(f) Calculate the ligand field stabilization energies (LFSE) of the octahedral complexes formed
by Co2+ and
(i) Cl- (weak field ligand), (ii) CN- (strong field ligand) (6 marks)
(ii) Arrange these complexes in their order of increasing stability? (1½ marks)
3. (a) (i) Deduce the type of hybridization in [Co(NH3)6]3+ and [Fe(H2O)6]2+ (6 marks)
(ii) Calculate spin only magnetic moment for the two complexes (4 marks)
(iii) Assuming the complexes are in octahedral geometry, show the distribution of d-
electrons in t2g and eg orbitals. (2½ marks)
(b) Name the following complexes:
(i) [Co(NH3)5CO3]Cl
(ii) [Cr(NH3)6][Co(CN)6]
(iii) K[Co(NH3)2(NO2)4]
(iv) Na[PtBrCl(NO2)(NH3)]
(v) [Ni(NH3)5(H2O)][Co(NO2)6]2 (5 marks)
(c) Use example to explain the following type of isomerism:
(i) linkage isomerism
(ii) ligand isomerism
(iii) geometrical isomerism (6 marks)
4. (a) Draw the energy level splitting diagrams and show the occupancy of the d-orbitals by
electrons in the following cases.
(i) d6 octahedral high-spin
(ii) d7 octahedral low-spin
(iii) d6 tetrahedral
(iv) d9 octahedral high-spin (8 marks)
(b) Calculate the crystal field stabilization energies in terms dq for a d system in octahedral and
8

tetrahedral complexes. (4½ marks)

(c) Predict the expected geometry in the table below:
Type of Geometry
hybridization
sp
sp2
sp3
dsp2
d2sp3
(5 marks)

4
 (d) State the d state of the central metal and predict the shape of the following complexes:
(i) [CoCl6]2- (ii) [Ni(CN)4]2- (iii) [Zn(NH3)5]2+ (6 marks)
5 (a) Write molecular orbital configuration and determine the bond order for the following
molecules
(i) N2+ (ii) C22- (iii) Ne2- (9 marks)
(b) What do you understand by Jahn-Teller effect? (2½ marks)
(c) Briefly discuss and show the structural properties of each of the following ternary
transition metal oxides:
(i) Fe3O4 (ii) Co3O4 (iii) Mn3O4 (6 marks)
(d) Give the partial molecular orbital (MO) diagram of an octahedral complex with
(i) σ-donor ligand (ii) π-donor ligand (iii) π-acceptor ligand (6 marks)

5
 COVENANT UNIVERSITY
CANAANLAND, KM 10, IDIROKO ROAD
P.M.B 1023, OTA, OGUN STATE, NIGERIA.
TITLE OF EXAMINATION: B.Sc EXAMINATION
COLLEGE: Science and Technology
SCHOOL: Natural and Applied Sciences
DEPARTMENT: Chemistry
SESSION: 2015/2016 SEMESTER: ALPHA
COURSE CODE: CHM 211 Marking guide CREDIT UNIT: 2
COURSE TITLE: Basic Inorganic Chemistry TIME: 2 HOURS
INSTRUCTION: Attempt 3 questions in all.

Answers
1. (a) The trend of IE in 3d is that higher oxidation states are less stable (more strongly
oxidizing) compared with the 4d and 5d series. For example, in group 7 is much more
strongly oxidizing than and in group 8. FeO4 is unknown but RuO4 and OsO4 are stable.
(4½ marks)
(b) (i) The bond-strength trend Cr≪Mo<W is the reverse of that normally found in main
groups. Its influence can be seen in the atomization enthalpies of the elements, reflecting
the strength of bonding in the metallic state. (2 marks)
(ii) Tunsgen, W. This is because it has a very high atomization energy reflected in its
extremely high melting and boiling points, a property important in applications such as
electric light bulb filaments. (2 marks)
(iii) The Cr3+/Cr2+ couple is more reducing than expected from its third IE as a result of the
large reduction of LFSE between Cr3+ (d3) and Cr2+ (d4).
Cr3+ = 3d3 = (t2g)3 = −6/5 Δo; Cr2+ = 3d4 = (t2g)4 = −8/5 Δo (2 marks)
(c) (i) A = MnO2 (1 mark) B = 𝑀𝑛𝑂4− (1 mark)
(ii) Mn4+ eg Mn7+ eg
4+ 3
Mn = Ar 3d 0
Mn7+ = Ar 3d
t2g
t 2g
(1 mark) (1 mark)

(iii) Since Jahn-Teller effect deals with distortion in the regular octahedral crystal lattice as
a result of unequal occupation of the t2g levels none of these, Mn4+ or Mn7+ will be
affected. (3 marks)

6
(d)
(i)

eg
Cl P 2+
Ni
Ni = Ar 3d8 (2 marks)
Cl
P t2g

(ii) O
eg
C Pd = Kr 5s2 4d8 (2 marks)
Pd C O t2g
C
C
O
O

(iii) I 2-
eg
Co Co2+ = Ar 3d7 (2 marks)
I I t2g
I

2. (a) In the 𝐹𝑒𝑂42− + 8𝐻 + + 4𝑒 − → 𝐹𝑒 2+ + 4𝐻2 𝑂;

Increasing the pH (and hence decreasing H+ concentration) will favour the left-hand side and so lower the
redox potential, Thus some high oxidation states are more accessible in alkaline than in acid solution. (3
marks)
(b) G is [(𝐻2 𝑂)5 𝐹𝑒 − 𝑂 − 𝐹𝑒(𝐻2 𝑂)5 ]4+ (3 marks)
1 1
(c) X = 2𝐻 + (1 2 𝑚𝑎𝑟𝑘) 𝑌 = 𝐶𝑟2 𝑂72− (1 2 𝑚𝑎𝑟𝑘)
(d) 2 Hard anionic ligands: F-, I- (2 mrks) 1 chelating ligand: ethylenediaminetetraacetic acid (EDTA) (1
mark)
(e) (i) [TiF6]2−, (1 mark) (ii) [VF6]−, (1 mark) (iii) [FeF6]3− (1 mark) and (iv)
O OH
H2 O O
L O- N
Co O-
N OH (1 mark)
L O O
OH 2

(f)

eg
2+ 7
Co = Ar 3d
t2g

Cl 4-
(i) (t2g)5= 5 x -2/5 = - 10/5
Cl Cl
(eg)2= 2 x 3/5 = 6/5
Co 3 marks
LFSE = 6/5 - 10/5 = - 4/5 o
Cl Cl
Cl

7
 eg
Co2+ = Ar 3d7
t 2g

(ii) NC 4-
(t2g)6 = 6 x -2/5 = - 12/5
CN NC
(eg)1= 1 x 3/5 = 3/5
Co LFSE = -12/5 + 3/5 = -9/5 o
3 marks
CN NC
NC

(iii) Order of increasing stability: [CoCl6]4- < [Co(CN)6]4- (1½ marks)

(3) 1. [Co(NH3)6]3+ Co--------- d6

∆

3d 4S 4p

d2Sp3 Hybridization

[Fe(H2O)6]2+ Fe= d6

3d 4S 4p

Sp3d2 hybridization

ii. For [Co(NH3)6]3+ n =0

using 𝜇 = √𝑛(𝑛 + 2)𝐵𝑀
𝜇 = 0 𝐵𝑀

For [Fe(H2O)6]2+ n= 4

8
 𝜇 = √4(4 + 2)𝐵𝑀
=√4(6)𝐵𝑀
=2√6 𝐵𝑀

iii.

1. Pentaaminecarbonatocobalt(I)chloride
2. Hexaaminechromium(ll)hexacyanocobaltate(ll)
3. Pottasiumdiamminetetranitrocobaltate(III)
4. Sodiumamminebromochloronitrito-N-platinate(II)
5. Pentamineaquanickel(II)hexanitrocobaltate(II)

Linkage Isomerism eg.

[Co(NH3)5(ONO)]Cl2 and Co(NH3)5(NO2)]Cl2

Ligand Isomerism eg.

[Co(pn)2Cl2]Cl and [Co(tn)2Cl2]Cl

Geometrical Isomerism eg.

and

9
4. (a) Draw the energy level splitting diagrams and show the occupancy of the d-orbitals by
electrons in the following cases.
(i) d6 octahedral high-spin

(ii) d7 octahedral low-spin

(iv) d6 tetrahedral

(v) d9 octahedral high-spin

(8 marks)
(b) Calculate the crystal field stabilization energies in terms of ∆ for a d system in octahedral
8

and
tetrahedral complexes.

10
 (4½ marks)
(c) Predict the expected geometry in the table below:
Type of Geometry
hybridization
sp linear
2
sp Triangular
planar
sp3 tetrahedral
2
dsp Square
planar
d sp
2 3
octahedral
(5 marks)
(d) State the d state of the central metal and predict the shape of the following complexes:
(i) [CoCl6]2-
3d5= octahedral
(ii) [Ni(CN)4]2-
3d8 = tetrahedral or square planar

(iii) [Zn(NH3)5]2+
3d10 = tetrahedral pyramidal
(6 marks)

5 (a) (i) Fe3O4,

Fe2+ (3d6) has an octahedral preference whereas Fe3+ (3d5) has none, and this compound has the
inverse spinel structure where Fe2+ is octahedral and Fe3+ is present in both octahedral and
tetrahedral sites.

11
 (2 marks)

b. (ii) Co3O4
The low-spin 3d6 ion Co3+ has a very strong octahedral preference and the normal spinel structure
is found with all Co3+ in octahedral sites and Co2+tetrahedral

(2 marks)

(iii) Mn3O4
Is also based on the normal spinel structure, but with a tetragonal distortion as expected for the
sites occupied by Mn3+ (3d4).

(2 marks)

(c)

(2 marks) (2 marks) (2 marks)

12
COURSE CODE: CHM211
COURSE TITLE: BASIC INORGANIC CHEMISTRY
CHM211 TUTORIAL
Transition Metal/Coordination Chemistry Tutorial Questions

1) a. Write the electronic configuration for each of the following transition metal
atoms and ions. Use [Ar] to represent the argon core configuration: 1s2, 2s2, 2p6, 3s2,
3p6.

Cu

Mn3+

Ni2+

Co

b. Indicate the coordination number about the metal and the oxidation number of the metal in

each of the following coordination compounds and complexes:

[MnO4]- K[CuCl2] Na4[Co(C2O4)2Br2] [Cr(edta)]-

Coordination No.

Oxidation No.

c. Give the correct IUPAC name for each of the following coordination compounds:

Na2[Ni(CN)4]

13
 [Mn(en)2I2]ClO4

2) Give the indicated isomers for each of the following coordination compounds and
complexes.

a. structural formula for the linkage isomer of [Cr(H2O)5(NO2)]I

b. structural formula for the coordination-sphere isomer of

[Co(o-phen)2(NH3)(SCN)]Cl

c. drawing of all possible stereoisomers of the octahedral complex,

[Fe(en)(C2O4)Br2]-

d. drawing of all possible stereoisomers of the square planar complex, [Pd(PPh3)2BrCl]

(PPh3 = triphenylphosphine, a monodentate ligand that bonds through the P atom.)

3) For each of the following sets, indicate the complex you would expect to absorb the shorter
wavelength (higher energy) visible light.

a. [Fe(NH3)6]3+ [FeF6]3- [Fe(CN)6]3-

b. [Co(en)3]3+ [Co(o-phen)3]3+ [Co(NH3)6]3+

4) Draw the crystal field d orbital energy level diagram, show the placement of d electrons for each
of the following complexes:

a. [Mn(C2O4)3]3- (octahedral geometry)

b. [Fe(o-phen)3]2+ (octahedral geometry)

5) Solutions of the following M3+ complexes are colored in aqueous solution: [MF6]3-, [M(en)2F2]+,
[M(en)3]3+, and [M(en)F4]-. The colors observed are green, red, orange, and violet. Based on the
spectrochemical series, match the color to the complex.

14
 Answers for Transition Metal/Coordination Chemistry tutorial Questions

1. a. Cu = [Ar]3d104s1

Mn3+ = [Ar]3d4

Ni2+ = [Ar]3d8

Co = [Ar]3d74s2

b.

[MnO4]- K[CuCl2] Na4[Co(C2O4)2Br2] [Cr(edta)]-

Coordination No. 4 2 6 6

Oxidation No. +7 +1 +2 +3

c. sodium tetracyanonickelate(II)

bis(ethylenediamine)diiodomanganese(III) perchlorate

2. a. [Cr(H2O)5(ONO)]I

b. [Co(o-phen)2(NH3)Cl]SCN

c.

d.
Cl PPh3 Cl PPh3

Pd Pd

Br PPh3 Ph3P Br

15
3. a. [Fe(CN)6]3-

b. [Co(o-phen)3]3+

4. a. b.

5. [MF6]3- = green

[M(en)2F2]+ = red

[M(en)3]3+ = orange

[M(en)F4]- = violet

16
 CHM211
Transition Metal/Coordination Chemistry Tutorial Questions

1) a. Write the electronic configuration for each of the following transition metal
atoms and ions. Use [Ar] to represent the argon core configuration: 1s2, 2s2, 2p6, 3s2,
3p6.

Cu

Mn2+

Cr3+

b. Give the coordination and oxidation numbers for the transition metal atom in each
of the following coordination compounds.

Na[Co(edta)] K[Ag(CN)2] [Ni(NH3)4]Br2 [Co(en)2Br2]

Coordination No.

Oxidation No.

2) a. Name each of the following coordination compounds using the IUPAC rules.

[Mn(H2O)5Cl]Br

Na3[FeF6]

b. Write the correct structural formula for the isomers indicated for each of the
following coordination compounds. Note that a structural formula is a chemical
formula that shows how the atoms are bonded to one another in a molecule.

17
 Na[FeCl4] is a structural formula.

linkage isomer of [Co(NH3)5(ONO)]Cl

ionization isomer of [Fe(NH3)5I]Br2

3) Draw all possible stereoisomers for each of the following complexes. Label the
diastereoisomers as cis or trans. If no stereoisomers are possible, indicate this fact and draw the
only structure possible.

[Ni(NH3)2Cl2] (square planar)

[Fe(en)2Br2]+

4) Using crystal field theory, draw the crystal field d orbital energy level diagram for each of the
following complexes by assigning electrons to 3d orbitals.

[Co(en)2]2+ (square planar)

[FeF6]3- (octahedral)

5) For the following complex, draw an orbital diagram for the isolated metal ion. Then,
using valence bond theory, draw the orbital diagram for the metal ion in the complex and
indicate the geometry of the complex. Also, clearly indicate which hybrid orbitals the
metal uses for covalent bonding with the ligands.

[FeCl4]- (5 unpaired electron)

6) The colors observed for the four complexes of metal ion M3+, [M(en)3]3+, [M(ox)3]3-, [MF6]3-, and
[MI6]3-, are blue, green, violet, and yellow. Match the color to the complex.

18
 Answers for Transition Metal/Coordination Chemistry tutorial Questions

1. a. Cu = [Ar]3d104s1

Mn2+ = [Ar}3d5

Cr3+ = [Ar]3d3

b.

Na[Co(edta)] K[Ag(CN)2] [Ni(NH3)4]Br2 [Co(en)2Br2]

Coordination No. 6 2 4 6

Oxidation No. +3 +1 +2 +2

2. a. pentaaquachloromanganese(II) bromide

sodium hexafluoroferrate(III)

b. [Co(NH3)5(NO2)]Cl

[Fe(NH3)5Br]BrI

3. [Ni(NH3)2Cl2] Cl Cl

H3N Ni NH3 Cl Ni NH3

Cl NH3
trans cis

19
 [Fe(en)2Br2]+

cis #1 cis #2 trans

4.

[Co(en)2]2+ (square planar)

[FeF6]3- (octahedral)

20
5. Fe3+ [Ar]      __ __ __ __ __ __ __ __ __

3d 4s 4p 4d

FeCl4- [Ar]          __ __ __ __ __ tetrahedral

3d sp3 4d

6. [M(en)3]3+ = yellow

[M(ox)3]3- = violet

[MF6]3- = blue

[MI6]3- = green

21
COURSE CODE: CHM212
COURSE TITLE: BASIC PHYSICAL CHEMISTRY

TUTORIAL QUESTIONS CHM 212

1. Starting from the kinetic gas equation derive

(i) Boyle’s law (ii) Charles’ law (iii) Avogadro’s law
ANSWER

i) Boyle’s Law

According to the postulates of the Kinetic Theory, K.E.  T

1
i.e nmu 2  T
2

1
or nmu 2 = K  T
2

1 21  2
But PV = nmu 2 =  nmu 2   K T
3 32  3

= constant x T

That is, at constant temperature PV = Constant.

This is Boyle’s Law.

ii) Charle’s Law

2
PV = K T
3

 2 K 
:. V =  T
 3 P 

22
:. At constant pressure

V = Constant x T

i.e. At constant pressure, V is directly proportional to the absolute temperature, T. This is Charle’s
law.

iii) Avogadro’s Principle

At the same pressure and volume

P1V1 = P2V2

1 1
:. n1m1 u12  n2 m2 u22
3 3

2 1  2 1 
or n1  m1 u12   n2  m2 u22  …………………………. 1
3 2  3 2 

At constant temperature, the average K.E. per molecule will be the same

2 2
:.
n1  n2
3 3
or n1 = n2

That is, at the same pressure and temperature equal volume of all gases will contain the same
number of molecules. This is Avogadro’s Principle. The Avogadro’s number N = 6.023 x 1023 is
the actual number of molecules in one gram mole of the gas.

2. A 10.0 L flask contains 64g of oxygen at 27oC. Calculate the pressure using,
(i) Van der waal’s equation and (ii) ideal gas equation. Given that a = 4.17 L atm mol-
2
and b = 0.037 L mol-1

Answer

i)4.808 atm (ii) 4.938 atm

23
 3. Derive the Kinetic gas equation for an ideal gas

Consider a cubic container of size l cm containing a total of N molecules of gas. Assume the
velocity u of the molecule is u cms-1. This can be decomposed into three components along the
coordinates axes

i.e. u = ux + uy + uz

and u2 = u2x + u2y + u2z

Consider one molecule of the gas starting from face A and moving in the x direction with a velocity
ux towards the opposite face. When it hits this face it rebounds and travels back to strike A.

:. Total distance travelled during this process = 2l cm

No of collisions per unit time per molecule at face A = distance per unit time travelled

Distance between collisions

ux
= ……………………..(1)
2l

24
Since the collision is elastic, change of momentum per collision per molecule at face A = mux – (-
mux) = 2mux …………………………………………………………..(2)

:. Change in momentum per unit time per molecule at face A = (1) x (2)

ux
= x 2mux
2l

2
mu x
=
l

2
Nmu x
:. Total average change in momentum per unit time for N molecule = ……(3)
l

where u 2 x = the average of the square of the velocities in the x direction.

Alternative definition of force, F is the time rate of change of momentum

2
Nmu x
:. Total force exerted by the N molecules on face A =
l

Force
But P =
Area

:. P at face A due to the N molecules is given by

2 2 2
Nmu x Nmu x Nmu x
P=  2
 …………………………………………………(4)
l.( Area) l.l v

where v = volume of the cube

Since the motions of the molecules are completely random,

ux  u y  uz
2 2 2

u 2  u x  u y  u z  3u x
2 2 2 2
But

25
 u2

2
:.
ux …………………………………………………..(5)
3
where u 2 is the mean square velocity for all the molecules in the given gas.

Substituting equation (5) into (4)

Nmu 2
P= or
3V

1
PV =
Nmu 2
3

1
Alternatively, PV = nmu 2 where n of the number of molecules of gas.
3

This equation is perfectly general regardless of the shape of the container.

4. What are the assumptions of kinetic theory of gases

 Gases are composed of separate, tiny particles called molecules dispersed
throughout the container. The actual volumes of the molecules is negligible
compared to the total volume of the gas. Molecules are identical.
 Gas molecules are in constant, rapid, straight line motion (which means that gas
molecules have kinetic energy ( KE = ½ mv² ) at high velocities.
 The collisions between molecules are completely elastic when molecules collide,
there is no loss of kinetic energy of a molecule during collision.
 The molecules of a gas have no attraction or repulsion for each other therefore gas
molecules can move freely independent of each other.
 The pressure of a gas is caused by the hits recorded by molecules on the walls of
the container.

26
 5. Calculate the root mean square velocity at 27oC
Answer
41.24 m sec-1

6. What do you understand by the distribution of molecular velocities of gas? Illustrate

your answer with the help of a diagram.

Answer

Distribution of molecular Velocities (in 3 Dimensions)

All molecules do not have the same velocity and consequently the same K.E, there is
always redistribution of both velocity and energy due to collisions. Maxwell and Boltzmann have
shown that the actual distribution of molecular velocities depends on (i) temperature & (ii)
molecular mass of the gas and this distribution is given by

3  Mu 2 
 
dnu  M  2   2 RT  2
 4   e u du ………………………………………. (1)
n  2RT 

Maxwell – Boltzmann distribution law for molecular velocities.

Where dnu is the number of molecules out of a total of n having velocities between u and u + du.

dnu
= fraction of the total number of molecules
n

M = molecular mass, T = temperature of the gas

Rewriting equation 1:-

3  Mu 2 
 
1 dnu  M  2  2 RT  2
 4   e  
u
n du  2RT 

27
20 x 10-4
298k
T1

T1 > T2
1 dnu -4
10 x 10
n du
T2
1500k
-4
5 x 10

0 500 1000 2500

u ms-1

Note: 1. At low temperature, spread of velocity is narrow.

2. At high temperature, there is a wider spread of velocities and the max. peak shifts to
higher velocity.

Explanation for the Shapes of the Curves

At low temperature, the molecule possess low energy and hence most of them will move
at low speed. The most probable speed will therefore be small which implies that the maximum of
the curve will occur early with relatively high probability since most molecules are moving at
about this speed.

The fall from the maximum is very sharp, since the energy is too low for high speed of
molecules. As the temperature increases, the energy increases and molecules move faster. This
will shift the maximum to the right. Also, more molecules now move with higher speed which also
slows down the fall of the curve to zero probability. Hence, although the average speed is higher
than at the low temperature, it is spread over more gas molecules and the effect will be to flatten
the curve.

28
7. Calculate the total pressure in a mixture of 4 g of oxygen and 3 g of hydrogen confined in a total
volume of one litre at 0oC.

Answer: 25.18 atm

8. For the reaction

2A(g) + B (g) 3C(g)

a) Determine the expression for the rate of the reaction with respect to each of the reactants
and products
b) When A is decreasing at a rate of 0.100M/s, How fast is B decreasing?
9. Consider the data showing the initial rate of the reaction (A Product). What is the
concentration of A?
b. What is the order of reaction?
c. What is the rate law for the reaction including the value of the rate constant k?

[A] M Initial Rate (M/s)

0.100 0.053
0.200 0.210
0.300 0.473

10. For a first order reaction A Product, the half life is 726s. Starting with a concentration
of 0.600M, what would the concentration be after 726s? What is the numerical value of k?
11. Compound A decomposes to form B and C the reaction is first order. At 250C the rate
constant for the reaction is 0.450 s-1. What is the half-life of A at 25 oC?
12. For a reaction mechanism

𝐻2 + 2𝑁𝑂 → 𝑁2 + 𝐻2 𝑂2 𝒔𝒍𝒐𝒘

𝐻2 𝑂2 + 𝐻2 → 2𝐻2 𝑂 𝒇𝒂𝒔𝒕

What is the rate law?

Solution
29
 8.
a) Rate =
𝟏 ∆[𝑨] ∆[𝑩] 𝟏 ∆𝑪
− = − =
𝟐 ∆𝒕 ∆𝒕 𝟑 ∆𝒕
∆[𝐴] 0.100𝑀 ∆[𝐵] ∆𝐶
bi) = − 𝑓𝑖𝑛𝑑 𝑎𝑛𝑑
∆𝑡 𝑠 ∆𝑡 ∆𝑡

Substitute value and solve for the two desired values

1 ∆[𝐴] −0.100𝑀 ∆[𝐵]
− = − = −𝟎. 𝟎𝟓𝟎𝟎𝑴𝒔−𝟏
2 ∆𝑡 𝑠 ∆𝑡
1 ∆[𝐴] −0.100𝑀 1 ∆𝐶 ∆𝐶
bii) − = = = 0.150ms-1
2 ∆𝑡 𝑠 3 ∆𝑡 ∆𝑡

0.210𝑀/𝑠 𝑘(0.200𝑀)𝑛
9. =
0.053𝑀/𝑠 𝑘(0.100𝑀)𝑛

= 3.9623 = 2n ≈ 4

Therefore n=2 because 22 =4

Comparing the first and the last data sets would give
0.473𝑀/𝑠 𝑘(0.300𝑀)𝑛
=
0.053𝑀/𝑠 𝑘(0.100𝑀)𝑛

= 8.9245 = 3n

≈9 = 3n

Therefore n=2 because 9 = 32

Rate = k[A]2
𝑅𝑎𝑡𝑒 0.210𝑀/𝑠
k= =
[𝐴]2 (0.200𝑀)2

5.25 M-1. s-1

Rate = 5.25M -1 * s-1[A]2

30
10. t1/2 = 726
ln[Ao]= 0.600M
ln[A] = ?
k =?

a) ln (0.600M) – ln [A] = (9.55 X 10-4 X 726) = 0.3M

b) t1/2 = 0.693 / k
0.693 0.693
726 = = = 𝟗. 𝟓𝟓 𝑿 𝟏𝟎−𝟒
𝑘 726

𝟎.𝟔𝟗𝟑 𝟎.𝟔𝟗𝟑
11 . 𝒕𝟏/𝟐 = = =1.54 s
𝒌 𝟎.𝟒𝟓𝟎

12
𝐻2 + 2𝑁𝑂 → 𝑁2 + 𝐻2 𝑂2 𝑠𝑙𝑜𝑤

𝐻2 𝑂2 + 𝐻2 → 2𝐻2 𝑂 𝑓𝑎𝑠𝑡

Overall reaction

𝐻2 + 2𝑁𝑂 → 𝐻2 𝑂2 + 𝑁2
2 2
Rate = [H2] [NO]

31
PART 2

2ND LAW OF THERMODYNAMICS

13. Calculate the change in entropy in melting of 2g ice at 0𝑜 𝐶 in S. I. units given that the heat
of fusion of ice is 80cal/g.
𝑞
∆𝑆 = 𝑇
q for 2 g of ice = 80 ×2 = 160 cal.
160 𝑐𝑎𝑙
∆𝑆 = = 0.586 cal K-1
273
1 cal = 4.186 J
0.586 ×4.186
Therefore 0.586 cal/ K will be = 2.452 JK-1
1
14. Calculate the entropy increase in the evaporation of 2mol of water at 100 degree centigrade
in S. I. units given that the heat of vaporization of water at 100 degree centigrade is
540cal/g.
∆𝐻 for 2 moles of water = 540 × 36g = 19440 cal
𝑞 19440
∆𝑆 = 𝑇 = 373 = 52.11 cal K-1
1 cal = 4.186 J
52.11 ×4.186
Therefore 52.11 cal K-1 will be 1
ANS: 218.16 JK-1
15. Write notes on the limitations of the first law of thermodynamics
ANS: The first law of thermodynamics does not indicate the direction in which the change
can occur. For Example, when a moving car is stopped by applying brakes, work done
against friction is converted into heat. When the car cools down, it does not start moving
with the conversion of all its heat energy into mechanical work. The first law of
thermodynamics gives no idea about the extent of change. The first law of thermodynamics
gives no information about the source of heat. i.e. whether it is a hot or a cold body.
16. At 373K the entropy change for the transition of liquid water to steam is 109JK-1mol-1.
Calculate the enthalpy change for the process.
∆𝐻
∆𝑆 = 𝑇 . ∆𝐻 = ∆𝑆 ×𝑇 = 109 ×373 𝐾
ANS: 40.657 kJ mol-1
17. 2mol of an ideal gas expand reversibly from a volume of 4 cubic decimetre to 40 cubic
decimetre at a temperature of 25 degree centigrade. Calculate the change in entropy given
that R = 8.314 Joules per mol per Kelvin and 1 litre = 1 cubic decimetre.
40
∆𝑆 = 𝑛𝑅2.303 log
4
= 2 × 8.314 2.303 = 38.29 JK-1
ANS: 38.29 J/K
18. Calculate the change in entropy accompanying the heating of one mole of helium gas,
assumed ideal, from a temperature of 27𝑜 𝐶 to a temperature of 820𝑜 𝐶 at constant pressure
3
given that 𝐶𝑉 = 2 𝑅.
At constant pressure, ∆S = 2.303× n× CP log (T2/ T1)

32
 CP - 𝐶𝑉 = R,
3
Cp - 2R = R
5
Cp = 2 R,
5 820
∆S = 2.303 × 1× 2 R × log = 70 .96
27

ANS: 70.96 J/K

19. 2mol of an ideal monoatomic gas expand reversibly from a volume of 2litres and
3
temperature of 289K to a volume of 20litres and temperature of 240K. Assuming 𝐶𝑉 = 2 𝑅,
calculate the entropy change for the process.
∆S = 2.303 n 𝐶𝑉 log T2/T1 + 2.303 R log v2/ v1
3 240 20
∆S = 2.303 × 2× 2 × 8.314 × log 289 + 2.303 × 8.314× log 2
ANS: 14.512 J/K
20. Four moles of an ideal gas expand isothermally from 1 litre to 10 litres at 300 K. Calculate
the change in free energy of the gas.
∆G = 2.303 nRT log V1 / V2
1
= 2.303 × 300 × 4 × 8.314 × log 10
ANS: - 22.9765 kJ

33
 COVENANT UNIVERSITY
CANAANLAND, KM 10, IDIROKO ROAD
P.M.B 1023, OTA, OGUN STATE, NIGERIA.
TITLE OF EXAMINATION: B.Sc. EXAMINATION
COLLEGE: Science and Technology
SCHOOL: Natural and Applied Sciences
DEPARTMENT: Chemical Engineering
SESSION: 2015/2016 SEMESTER: ALPHA
COURSE CODE: CHE 212 CREDIT UNIT: 2
COURSE TITLE: Chemistry for Non-major I TIME: 2 HOURS
INSTRUCTION: Attempt 3 questions in all.

1.(a) State the first and the third laws of thermodynamics . How are they expressed
mathematically? (3½ marks)
(b) Write short note on the following terms:
(i) Spontaneous process (ii) State function (iii) Reversible process
(iv) Intensive property (v) Clausius Statement (10 marks)
(c) Gibbs free energy in terms of the state parameter is given as,
dG = VdP – SdT,
𝑑𝐺 𝑑𝐺
Derive the expression: (𝑑𝑇 )p = -S and (𝑑𝑃 )T = V (7marks)
o
(d) 14 g of N2 gas expands reversibly from 2.5 litres to 18 litres at 15 C. Calculate ∆S.
(3 marks)

2.(a) (i) Define Gibbs free energy? (1½ mark)

(ii) Comment on the spontaneity of the process for which
∆H < 0, ∆S > 0 and ∆H > 0, ∆S > 0 (3 marks)
(iii) Calculate the free energy and entropy change per mole when liquid water boils at 1
atm, given that ∆Hvap for water = 2.0723 kJ/g (3 marks)
(b). Calculate the entropy change when
(i) 2 moles of an ideal gas undergoes expands from -5oC (3 atm) to -10oC (1.5 atm). Given
that Cv = 1.5R (4 marks)
(ii) Expands isothermally to 5 times of its initial volume. (3 marks)
o o
(c). Gibbs free energy for a reaction at 25 C and 35 C are -25 kJ and - 28 kJ respectively.
Calculate ∆S and ∆H (5 marks)
(d). Explain the following terms
(i) intensive property ( 2 marks)
(ii) kelvin’s statement ( 2 marks)

34
3.(a) (i) Draw and indicate the type of hybridization in [Co(NH3)6]2+ and [Fe(H2O)6]2+
(6 marks)
(ii) Calculate spin only magnetic moment for the two complexes (4 marks)
(iii) Assuming the complexes are in octahedral geometry, show the distribution of d-
electrons in t2g and eg orbitals. (2½ marks)

(b) Name the following complexes:

(i) [Co(NH3)5CO3]Cl
(ii) [Cr(NH3)6][Co(CN)6]
(iii) K[Co(NH3)2(NO2)4]
(iv) Na[PtBrCl(NO2)(NH3)]
(v) [Ni(NH3)5(H2O)][Co(NO2)6]2 (5 marks)
(c) Write molecular orbital configuration and determine the bond order for the following
molecules: (i) N2+ (ii) C22- (iii) Ne2- (6 marks)

4.(a) Deduce the state of the d-orbital of the central metal in the following complexes. State its
magnetic property (paramagnetic or diamagnetic).
(i) [Fe(CN)6]4‐ (ii) [Co(NH3)6]3+ (iii) [Cr(NH3)6]2+ (7½ marks)
(b) Using IUPAC methods, write the formulas for the following complexes:
(i) Pentaamminenitrito-N-cobalt(III) (ii) Potassium tetracyanonickelate(II)
(iii) Pentaamminenitrito-O-cobalt(III) (iv) Hexaamminecobalt(III) sulphate
(v) Potassium tetrachloridopalladate(II) (5 marks)
(c) (i) Using Crystal Field Theory,show orbital occupancies for both weak and strong
octalhedral fields for Mn2+, Zn2+, Fe2+ and Co2+
(ii) Calculate spin only magnetic number in each case. (10 marks)

5.(a) What do you understand by the following?

(i) Spectrochemical series
(ii) Crystal field stabilization energy. (5 marks)
(b) Draw the energy level splitting diagrams and show the occupancy of the d-orbitals by
electrons in the following cases.
(i) d6 octahedral high-spin (ii) d7 octahedral low-spin
(iii) d6 tetrahedral (iv) d9 octahedral high-spin (8 marks)
Calculate crystal field stabilization energy in ∆ units for d octahedral low-spin
7

giving that 1 ∆ = 1000cm-1 (3 marks)

(c) What is the oxidation number of the metal in each of the following complexes:
i. [Co(NH3)6]Cl3 ii. [CoSO4(NH3)4]NO3 iii. [AlH4]-
4-
iv. [Cr(en)3]Cl3 v. [Fe(CN)6] (7½ marks)

35
 COVENANT UNIVERSITY
CANAANLAND, KM 10, IDIROKO ROAD
P.M.B 1023, OTA, OGUN STATE, NIGERIA.
TITLE OF EXAMINATION: B.Sc. EXAMINATION
COLLEGE: Science and Technology
SCHOOL: Natural and Applied Sciences
DEPARTMENT: Chemical Engineering
SESSION: 2015/2016 SEMESTER: ALPHA
COURSE CODE: CHE 212 Marking guide CREDIT UNIT: 2
COURSE TITLE: Chemistry for Non-major I TIME: 2 HOURS
INSTRUCTION: Attempt 3 questions in all.

CHE 212 MARKING GUIDE

1 (a) The first law of thermodynamics states that one form of energy can change into another
form but the total amount of energy remains the same. But the first law fails to indicate if the
process of change we specify, can occur or if so in what direction. The 1st Law of thermodynamics
does not give any information about direction of change. Yet experience shows that most natural
processes always tend to occur spontaneously in a direction which will lead to equilibrium e.g. flow
of heat (ii) electricity (iii) water (iv) gas.

dE = dq – dw

b. The 3rd law can be defined as every substance, element or compound has a finite entropy but at
absolute zero of temperature, the entropy may become zero and does become in the case of a

36
perfectly crystalline substance. The concept of entropy is a measure of orderliness or randomness
has lead to the conclusion that all substances in their normal crystalline state at the absolute zero
temperature would be in the condition of maximum orderly arrangement because all motion has
essentially ceased at 0K.

i. SPONTANEOUS PROCESS

A process which proceeds of its own accord, without any outside assistance, is termed a spontaneous
process. The reverse process which does not proceed on its own, is referred to as a non spontaneous
process. In general, the tedency of a process to occur naturally is called the spontaneity. Spontaneous
changes proceed until the system reaches an equilibrium state. They are irreversible.

Examples:

 Cliff jumping and mountain climbing.

 Heat flow from a hot ball to a cold one, never from cold to hot.
 When a vessel containing a gas is connected to another evacuated vesseL, the gas spreads
throughout spontaneiuoly unless the pressure is the same in both vessels. 2.5 mks
ii. Reversible Process
The process is reversible when the driving force is only infinitesimally (minutely) greater
than the opposing force, and the process can be reversed by increasing the force by an
infinitesimal amount. For a reversible process p  Pex is slightly greater than p the gas is
compressed. On the other hand of p is slightly greater than Pex, the gas will undergo
expansion.
A reversible process is a change of state such that
1. The change occurs in a sequence of steps, each of which is infinitesimally removed
from the preceding and succeeding steps.
2. The change occurs through a succession of equilibrium steps, each intermediate state
being an equilibrium state.
A reversible process must be carried out at a very slow rate for condition 2 above to
hold. This makes true reversible process in practice unattainable as such a process will
require an infinitely long time to go to completion. 2 mks
iii. Clausius statement
It is impossible for a cyclic process to transfer heat from a body at a lower temperature to
one at a higher temperature without simultaneous conversion of work into heat.
This implies that when work is used for the continuous transfer of heat from a lower
temperature to one at a higher temperature, some work must be wasted by direct conversion
into heat 2 mks
iv. State Function.
A state function does not depend on the path in which the process is performed instead it
depends only on the initial and final states.e.g internal energy of a system, temperature. An

37
 important characteristic of a state variable is that when the state of a system is altered, the
change in the variable depends on the initial and final states of the system. 2 mks
v. Intensive Property
An intensive property is a bulk property, meaning that it is a physical property of a system
that does not depend on the system size or the amount of material in the system. Examples
of intensive properties include temperature, refractive index, density, and hardness of an
object. 2 mks

1d.
∆S = 2.303 n 𝐶𝑉 log T2/T1 + 2.303 R log v2/ v1……………1.5mk.
3 240 20
∆S = 2.303 × × 2 × 8.314 × log 289 + 2.303 × 8.314× log 2 …………. 3 mks
= 16.82JK-1………………….1.5mks.
C.
G= H – TS
and H = E + PV ( first law of thermodynamics)
G = E + PV – TS
Differentiating
dG = dE + PdV + VdP – TdS – SdT……….(i)
For an infinitesimal stage of a reversible process. dq = dE + dw
𝑑𝑞
Recall dS = 𝑇
dq = dE + PdV ( first law of thermodynamics)
Therefore TdS =dE + PdV…………(ii)
Substituting eqn. (ii) into (i) we have
dG= dE + PdV + VdP – dE - PdV – SdT
= VdP – SdT…………. (iii)
At constant pressure eqn (iii) becomes
dGp = -SdTp
𝑑𝐺
Or (𝑑𝑇 )p = -S………………………. (iv)……….
At constant temperature eqn (iii) becomes
dGT = VdPT
𝑑𝐺
Or (𝑑𝑃 )T = V………………………. (V)……
Eqn (iv) and (v) shows how free energy varies with temperature and pressure
respectively…………………………………..7.5 marks
2.

The second law of thermodynamics states that: whenever a spontaneous process takes place, it is
accompanied by an increase in the total energy of the universe.

∆Suniv = ∆Ssyst + ∆Ssurr

38
The second law, as stated above, tells us that when an irreversible spontaneous process occurs, the
entropy of the system and the surroundings increases.

In other words ∆Suniv > 0. When a reversible process occurs, the entropy of the system remains
constant. ∆Suniv =0. since the univers is always experiencing a change the second law can be restated
as: the entropy of the system is constantly changing.

NO 2

Gibbs Free Energy

The free energy (G) is defined as

G = H – TS

where H is the heat content or enthalpy of the system, T is its temperature and S its entropy. It is a
single valued function of thermodynamic state of the system and is an extensive property. (1.5 mk)

b. i Spontaneous 1 mk

ii. non spontaneous 1 mk

c. The enthalpy of vaporization with molecular weight of water = 18 g/mol is calculated as

∆H vap = 2.0723 × 18 = 37.30 Kj/mol

The entropy change is

∆H 37.30
∆S = = 373𝐾 kJ/mol = 0.1 kJ/mol (1.5 mks)
𝑇

The free energy is ∆G = ∆H - T∆S = 37.30 – 37.30kJ/mol = 0 (1.5 mks)

The system is at equilibrium

C. i Entropy change for this process is given by

𝑇2 𝑝1
∆S = 2.303C log 𝑇1 +2.303 R log 𝑝2 1mk
p

Cp = Cv + R = 1.5 R + R = 2.5R 1mk

∆S = 41.57 × - 0.01883 – 16.628 × - 0.693

∆S = 10.47 kJ/mol 2 mk
𝑇2 𝑣2
ii. ∆S = 2.303C log 𝑇1 +2.303 R log 𝑣1
v 1 mk

39
 𝑇2 5𝑣1
∆S = 2.303C log 𝑇1 +2.303 R log
v
𝑣1
∆S = 0 + 16.628 × 1.61 = 26.762 J/Kmol

D. According to Gibbs – Helmholtz equation

∆𝐺 ∆𝐺2− ∆𝐺1 −28 −25.5
∆S = ∆𝑇 = = = -5.35kJ/K 2.5 mks
𝑇2−𝑇1 308−298

∆H = ∆G + T∆S

∆H = -28 + 298(-5.35) = -1622.3kJ

d. It is impossible for a cyclic process to convert heat into work without simultaneous transfer
of heat from a body at higher temperature to one at lower temperature. This implies that in
the conversion of heat into work, some of the heat in a body at higher temperature must be
wasted by direct transfer to a body at a lower temperature. 2mks

ii. intensive property: These are properties which are independent of the quantity of matter
present in the system. For example temperature, pressure, density. 2mks

3.(a) (i) Draw and indicate the type of hybridization in [Co(NH3)6]3+ and [Fe(H2O)6]2+
(6 marks)
(3) 1. [Co(NH3)6]3+ Co--------- d6
∆

3d 4S 4p

d2Sp3 Hybridization

[Fe(H2O)6]2+ Fe= d6

3d 4S 4p

Sp3d2 hybridization
(ii) Calculate spin only magnetic moment for the two complexes (4 marks)

40
ii. For [Co(NH3)6]3+ n =0
using 𝜇 = √𝑛(𝑛 + 2)𝐵𝑀
𝜇 = 0 𝐵𝑀

For [Fe(H2O)6]2+ n= 4
𝜇 = √4(4 + 2)𝐵𝑀
=√4(6)𝐵𝑀
=2√6 𝐵𝑀

(iii) Assuming the complexes are in octahedral geometry, show the distribution of d-
electrons in t2g and eg orbitals. (2½ marks)

iii.

(b) Name the following complexes:

(i) [Co(NH3)5CO3]Cl
(ii) [Cr(NH3)6][Co(CN)6]
(iii) K[Co(NH3)2(NO2)4]
(iv) Na[PtBrCl(NO2)(NH3)]
(v) [Ni(NH3)5(H2O)][Co(NO2)6]2

6. Pentaaminecarbonatocobalt(I)chloride (5 marks
7. Hexaaminechromium(ll)hexacyanocobaltate(ll)
8. Pottasiumdiamminetetranitrocobaltate(III)
9. Sodiumamminebromochloronitrito-N-platinate(II)
10. Pentamineaquanickel(II)hexanitrocobaltate(II)
(c) Write molecular orbital configuration and determine the bond order for the following
molecules: (i) N2+ (ii) C22- (iii) Ne2- (6
marks)

41
(i) N2 =13 electrons
+

(𝜎1𝑠)2(𝜎 ∗ 1𝑠)2(𝜎2𝑠)2(𝜎 ∗ 2𝑠)2(𝜎2𝑝𝑥 )2(𝜋2𝑝𝑦2 = 𝜋2𝑝𝑧1)

Bond order = (bonding e- - antibonding e-)/ 2

= (9-4) /2 = 5/2 = 2.5

ii C22-= 14 electrons
(𝜎1𝑠)2(𝜎 ∗ 1𝑠)2(𝜎2𝑠)2(𝜎 ∗ 2𝑠)2(𝜎2𝑝𝑥 )2(𝜋2𝑝𝑦2 = 𝜋2𝑝𝑧2)
Bond order = (bonding e- - antibonding e-)/ 2

= (10-4) /2 = 6/2 = 3

(iii) Ne2- = 8 electrons

(𝜎1𝑠)2(𝜎 ∗ 1𝑠)2(𝜎2𝑠)2(𝜎 ∗ 2𝑠)2
Bond order = (bonding e- - antibonding e-)/ 2

= (4-4) /2 = 0

4.(a) Deduce the state of the d-orbital of the central metal in the following complexes. State its
magnetic property (paramagnetic or diamagnetic).
(i) [Fe(CN)6]4‐
Fe--- Fe2+ = 3d6 - It is paramagnetic
(ii) [Co(NH3)6]3+
Co3+ = 3d6 --- It is diamagnetic
(iii) [Cr(NH3)6]2+
Cr 2+ = 3d4 It is paramagnetic
(7½ marks)

2+
(b) CO (H2D)6

Co2+ 3d9 system

42
 3d9 4s 4p 4d

H20

Therefore the hybridization is 8p3d2

2+
CO (NH3)6

Cu2+ d6 system

3d 4s 4p

NH3

D2sp3 hybridization

Therefore, the hybridization is d2sp3

2+
FO (H2O)6

Fe2+ d6 system

3d 4s 4p 4d

43
Therefore, the hybridization is SP3D2

(ii) µs = n (n+2) BM

for Cu,2+n=1 µs = I(1+2)

µs = 3 BM

for Co2+ n=O

µs = O(O+1) BM

= OBM

for fe2+ n=4

µs = 4 (4+1) BM

= 20 BM

= 2 S BM

(iii) for Cu2+ - 3d9

(t2g)6 (eg) 3
44
 for Co2+ - 3d6

for fe2+ - 3d6

2+
(C) (i) Co (NH3)5NO2

(ii) K2 N1 (CN)4

2+
(iii) Co (NH3)5ONO2

(iv) Co (NH3)6 SO4 _+

(v) K2 Pd Cl4

5(ai) Using Jahn-Teller theorem Octahedral Cu2+ ion – d 9 system

(t2g)6 (eg)3

45
 There is one vacancy in eg orbitals in either dx2-y2 or dZ2 orbital. If the
2
geomethry is a regular octahedral nul, then the two configurations will be d x2-y2,
1
d Z2 and d1x2-y2, d2Z2 are not equal energy, thus eg level look like this

dZ2

eg

dx2-y2

ii. Ns = n(n+2)

(bi) 1- The theory regards as point charges or as point dispels

2- The bonding between the metal cation and ligands arise due to the
dectrostatic attraction between metal and ligands.
3- The interaction between the electrons of the cation and those of the ligands is
repulsive this lead to splitting of the d – orbitals.

4- CFT does not consider the overlapping between metal orbitals.

5- d – orbitals which are degenerate in a free metal ion have their

degeneracy destroyed by the approach of the ligands during complex
formation.

ii. dx2-y2

dxy

d Square planear

dZ2

46
 dxy, dyz.

dx2-y2 dz2 eg

d Octahedral

t2g

dxy dy2

dx –y2

dZ2

d distorted Octahedral

dxy

dx2 dy2

t2g

dxy dxz dx2

47
 eg

dx2-y2 dZ2

(c) Mn2+ - 3d5

High spin Low spin

eg eg

t2g t2g

Zn2+ - d8 Low spin High spin

eg eg

t2g t2g

Fe2+ - d5 eg eg

t2g t2g

48
Co2+ - d7 eg eg

t2g t2g

(ii) CF8E = for d8

6 x (-0.4) + 2x(0.6) D0

- 2.4 - 1.2 = - 1.2 D0

For d5 = 5 x (-0.4) + 0 x (0.6) D0

-2.0 D0

For d7 = 6 x (-0.4) + (1 x 0.6) D0

-2.4 + 0.6 D0

= - 1.8 D0

For d5 = 3 x (0.4) + (2x0.6) D0

= 1.2 + 1.2 D0 = O D0

49
 COVENANT UNIVERSITY

CANAAN LAND, KM 10, IDIROKO ROAD

P.M.B 1023, OTA, OGUN STATE, NIGERIA

COURSE CODE: CHE 212 UNIT: 2

COURSE TITLE: Chemistry for Chemical Engineering I.

1. Electronegativity decreases down the group and increases across the period in

Halogens: explain?

The trend as you move from left to right across a period in the periodic table,

the electronegativity increases due to the stronger attraction that the atoms obtain as

the nuclear charge increases. Moving down a group, the electronegativity decreases due to the

longer distance between the nucleus and the valence electron shell, thereby decreasing the

attraction, making the atom have less of an attraction for electrons or protons.

2. What are the uses of Halogens in Industries?

Answer:

In drug discovery, the incorporation of halogen atoms into a lead drug candidate results in
analogues that are usually more lipophilic and less water-soluble.

Halogens are used in the chemical, water and sanitation, plastics, pharmaceutical,

pulp and paper, textile, military and oil industries.

 Bromine, chlorine, fluorine and iodine are chemical intermediates, bleaching agents and
disinfectants.

 Both bromine and chlorine are used in the textile industry for bleaching and shrink-
proofing wool.

 Bromine is also used in gold mining extraction processes and in oil- and gas-well drilling.

 It is a fire retardant in the plastics industry and an intermediate in the manufacture of

hydraulic fluids, refrigerating and dehumidifying agents, and hair-waving preparations.

3. Some incandescent light bulbs are filled with argon gas.

50
 What is vrms for argon atoms near the filament, assuming their temperature is 2500 K?

Answer:

1.25×103m/s

4. (a) what is the average kinetic energy of a gas molecules at 20oc?

(b) Find the rms speed of a nitrogen molecule (N2) at this temperature?

Answer:

(a) 6.07 x 1021J

(b) 511 m/s

5. What are the chemical and physical characteristics of Transition metals and mention any

five of their major uses in Industries.

Answers

 they are good conductors of heat and electricity

 they form coloured compounds
 they can be hammered or bent into shape easily
 they formed complex ions
 they have variable oxidation states
 they are less reactive than alkali metals such as sodium
 they have high melting points - but mercury is a liquid at room temperature
 they are usually hard and tough
 they have high densities

Uses

 Transition metals are extremely useful metals on account of their physical or chemical
properties. For example ….
 Cast iron is used for man-hole covers because it is so hard wearing
 Copper is used in electrical wiring because it is a good conductor of electricity.
 Copper is used in domestic hot water pipes because it is relatively unreactive to water and
therefore doesn't corrode easily
 Zinc is used to galvanise (coat) iron or steel to sacrificially protect them from corrosion
 Compounds of copper, iron, chromium and cobalt are used to give bright colours to stained
glass
 Transition metals often form important alloys.
For example, iron in steel, zinc and copper in brass.

51
  Transition metals often make good catalysts for particular reactions. Examples of transition
metal catalysts are Iron in the Haber Process, Vanadium(V) oxide in the contact process
(making sulfuric acid), Nickel is used in the hydrogenation of vegetable oils.

Lanre

6. For the following reaction

N2 (g) + 3H2 (g) = 2NH3 (g)

The free energy changes at 25oC and 35 oC are – 33.089 and – 28.018 respectively.
Calculate the Heat of reaction.

Answer: 184.174 kJ

7. Calculate the entropy change involved in thermodynamic expansion of 2 moles of a gas

from a volume of 5 litres to a volume of 50 litres at 303K

Answer : 38.29 JK-1

8. Two moles of an ideal gas are allowed to expand reversibly and isothermally at 300K from
a pressure of 1 atm to a pressure of 0.1 atm. What is the change in Gibbs energy?

Answer: - 11.4882 kJ

9. What is a spontaneous process? Give relevant example

Describe the carnot cycle.

Answer: A chemical reaction or physical change is said to be spontaneous if it has

the potential to proceed of its own accord under the specified conditions. Spontaneous
changes proceed until the system reaches an equilibrium state. They are irreversible.

Examples:

a) Gas will expand from regions of higher pressures to region lower of pressures.

b) The running down of a tightly wound

52
 c) Evaporation of water from streets after a rainfall. Petrol will vaporize when exposed.
d) Dissolution of most solutes

10 What do you understand by a reversible and Irreversible process?

Answer

Reversible Process

The process is reversible when the driving force is only infinitesimally (minutely) greater
than the opposing force, and the process can be reversed by increasing the force by an infinitesimal
amount.

Pex P = Pressure of gas

For a reversible process p  Pex is slightly greater than p the gas is compressed. On the other hand
of p is slightly greater than Pex, the gas will undergo expansion.

A reversible process is a change of state such that

1. The change occurs in a sequence of steps, each of which is infinitesimally removed from the
preceding and succeeding steps.

2. The change occurs through a succession of equilibrium steps, each intermediate state being an
equilibrium state.

Irreversible Process

Irreversible process is simply defined as one which is not reversible.

53
Examples of Reversible and Irreversible Process

a) A gas in a cylinder equipped with a movable piston

Pex Pex

(B) Pex >> p

(A) Pex  p

In both cases A & B, the gas is expanded. In case A the piston is withdrawn at a very slow rate so
that time is allowed for the pressure and temperature of the gas to attain uniform value after each
change. Hence the expansion goes through a succession of equilibrium states. Therefore the overall
process can be considered reversible.

In case B the piston is withdrawn rapidly and no time is allowed for the pressure and
temperature of the gas to attain uniform values after each change. The temperature and pressure
vary throughout the gas. Hence the expansion does not go through a succession of equilibrium
states. Therefore, the overall process can be considered irreversible.

11. Predict the no. of unpaired electrons, the spin‐only magnetic moments at 25 OC for each of
the following.

a) [Fe(CN)6]4‐

b) [Ru(NH3)6]3+

c) [Cr(NH3)6]2+

d) [EuCl6]4‐

Ans.

a) Fe2+ is 3d6. Has 0 unpaired electron in l.s. complexes and thus the magnetic

moment would be close to 0 µB.

b) Ru3+ is 4d5. Has 1 unpaired electron in l.s. complexes and thus the magnetic moment would be
close to 1.73 µB.

54
c) Cr2+ is 4d4. Have 4 and 2 unpaired electrons in h.s. and l.s. complexes and thus the magnetic
moment would be close to 4.90 and 2.83 µB, respectively.

d) Eu2+ is 4f7. Has 7 unpaired electrons in h.s. complexes and thus the magnetic moment

would be close to 7.94 µB. The magnetic moments deviate considerably from the spin‐only values
because of strong spin‐orbit coupling. The f‐orbitals have so little overlapand interactions with
ligand orbitals.

12. Explain the Jahn‐Teller distortion in [Cu(H2O)6]2+

13. Predict the number of unpaired electrons, the magnetic moments at 25◦C for each of

the following

(a) [Fe(CN)6]4‐, (b) [Ru(NH3)6]3+, (c) [Cr(NH3)6]2+, (d) [EuCl6]4‐.

Ans:

a) [Fe(CN)6]4‐→ Fe2+→ 3d6.

Low spin complex → 0(zero) unpaired electron → μB= 0

(b) [Ru(NH3)6]3+ → Ru3+ → 4d5.

Low spin complex → one unpaired electron → μB= 1.73 BM.

(c) [Cr(NH3)6]2+ → Cr2+ → 3d4.

High spin complex → 4 unpaired electrons → μB = 4.90 BM.

Low spin complex → 2 unpaired electrons → μB = 2.83 BM.

(d) [EuCl6]4‐→ Eu2+ → 4f7.

High spin complex → 7 unpaired electrons → μB = 7.9 BM.

The f orbitals have so little overlap and interaction with ligand orbitals.

14. How many geometrical isomers are possible in the following coordination entities?

55
(i) [Cr(C2O4)3]3−

(ii) [Co(NH3)3Cl3]

15. Determine the configuration (in the form t2g megn or emt2n, as appropriate), the number of
unpaired electrons, and the ligand field stabilization energy as a multiple of ∆o or ∆T for each of
the following complexes using the spectrochemical series to decide, where relevant, which are
likely to be strong‐field and which weak‐field.

(a)[Co(NH3)6]3+ ; (b) [Fe(OH2)6]2+

Ans.

(a) [Co(NH3)6]3+

Since the NH3 ligands are neutral, this is a Co3+complex, so we are dealing with a d6 metal
ion. Although ammonia is in the middle of the spectrochemical series, a metal in the 3+ oxidation
state is past the middle of the metal series, so the combination is very likely to be a low‐spin
configuration, t2g6eg0. Indeed, octahedral d6 has S = 0 (no unpaired electrons) and is
diamagnetic. The LFSE is 6 × 0.4∆o = 2.4∆o. Note that this is the largest possible LFSE for an
octahedral complex.

(b) [Fe(OH2)6]2+

The iron ion in this octahedral complex with six neutral water ligands is in the 2+ oxidation state,
and water is low on the spectrochemical series. We certainly expect this d6 ion to be in a high
spin configuration, t2g4eg2, with S = 2. That is, it has four unpaired electrons and is strongly
paramagnetic. The LFSE is 4 × 0.4∆o – 2 × 0.6∆o = 0.4∆o. Note the much smaller LFSE
compared to the low spin d6 case discussed in (a).

16. Draw the structure of the following complexes:

a) trans‐diaquadichloroplatinum (II)

b) diamminetetra(isothiocyanato)chromate (III)

56
17. a. Sketch the two structures that describe most six‐coordinate complexes. Which is more
common?

b. What is the coordination number of the Au atom in K[Au(CN)2(SCN)2]?

18. a. What is the respective central‐metal oxidation state, coordination number, and the overall
charge on the complex ion in NH4[Cr(NH3)2(NCS)4]?

19. Using IUPAC norms write the formulas for the following:

(i) Tetrahydroxozincate(II)

(ii) Potassium tetrachloridopalladate(II)

(iii) Diamminedichloridoplatinum(II)

(iv) Potassium tetracyanonickelate(II)

(v) Pentaamminenitrito-O-cobalt(III)

(vi) Hexaamminecobalt(III) sulphate

(vii) Potassium tri(oxalato)chromate(III)

(viii) Hexaammineplatinum(IV)

(ix) Tetrabromidocuprate(II)

(x) Pentaamminenitrito-N-cobalt(III)

Answer

57
(i) [Zn(OH]2

(ii) K2[PdCl4]

(iii) [Pt(NH3)2Cl2]

(iv) K2[Ni(CN)4]

(v) [Co(ONO) (NH3)5]2+

(vi) [Co(NH3)6]2 (SO4)3

(vii) K3[Cr(C2O4)3]

(viii) [Pt(NH3)6]4+

(ix) [Cu(Br)4]2−

(x) [Co[NO2)(NH3)5]2+

20. Using IUPAC norms write the systematic names of the following:

(i) [Co(NH3)6]Cl3

(ii) [Pt(NH3)2Cl(NH2CH3)]Cl

(iii) [Ti(H2O)6]3+

(iv) [Co(NH3)4Cl(NO2)]Cl

(v) [Mn(H2O)6]2+

(vi) [NiCl4]2−

(vii) [Ni(NH3)6]Cl2

(viii) [Co(en)3]3+

(ix) [Ni(CO)4]

58
Answer

(i) Hexaamminecobalt(III) chloride

(ii) Diamminechlorido(methylamine) platinum(II) chloride

(iii) Hexaquatitanium(III) ion

(iv) Tetraamminichloridonitrito-N-Cobalt(III) chloride

(v) Hexaquamanganese(II) ion

(vi) Tetrachloridonickelate(II) ion

(vii) Hexaamminenickel(II) chloride

(viii) Tris(ethane-1, 2-diammine) cobalt(III) ion

(ix) Tetracarbonylnickel(0)

59