COLLEGE OF' CHEMICAL SCIENCES

Institute of Chemistry, Ceylon

Graduateship Examination in Chemistry ,2019
Level 3

C31003 - Energetics and Kinetics

C3513 - Energetics and Kinetics

TIME: TI{REE (03) IIOIIRSpIzs 15 min reading time

Answer all the questions
Number of questions: 05 Number of pages: 06

The Answers to each pffi A, B & C should be submitted separately with appropriately ooloured covers as
you will be instructed by the Supervisor. If this rubric is not correotly followed, 10% of the marks
obtained will be deducted in accordance with College policy.

Question Number Allocated Recommended time %, Mark

Marks duration (Minutes)
PART A
1 100 40 22.2
2 80 32 17.8
PART B
J 100 40 22.2
PART C
4 t20 48 26.7
5 50 20 11.1
Total 450 180 100

The use of a non-programmable electronic calculator is permitted. However, the memory on your

calculator must be erased before you enter examination hall.

a Mobile phones are not allorved.
o Graph papers and logarithm tables will be provided,

R: 8.314 J mol-1 K-1

Log. X :2.303log1s X
ke: 1.381 x t0-23 J K-r
C:3.0x108ms-l
Ne: 6.022 x 1023 mol-t
I bar : Pa: 105 N m-2
10s
h:6.63 x l0-3aJs
1 atm.:
1.01 bar
e:1.60210-re C
r = 3.142
 PART A
Answer all parts
(f ) (a) Starting from the basic thermodynarnic relationships

dG=Vdp-SdT and G=H-TS

first derive the Gibbs Helmholtz relationship

a(c) H
tt
ar\T ), r)
and then use it to derive the van't Hoff isochore:

dInKo _ N{o
dT RTz

the relationship between K, and Ad may be quoted withourt proof.

(b)The equilibrium constant, K, of the gaseous reaction

COCI2 e> CO + f,1,

io'r o
2?t ,/v{
.)
I
/' tt{
has been measured at a series of temperatures around 700 K as follows:

T K / 63s.7 670.4 686.0 722.2 760.2

Ke 0.01950 0.0441,4 0,07575 0.1971 0.5183

By plotting a suitable graph, obtain a value for Atf of the above reaction; explain any approximations
that you make. Use this value to obtain values of Ad and /S0 at 700 K.

R= 8.314 J K-1 mol-1 (100 marks)

tl
y'n l, l, ' a
Answer all parts
(2) (aS (i) Starting from Arhenius equation show that the molar enthalpy of activation for a
unirnolecular reaction , L# H is given by (Eo - RD" Here Eo is the activation energy of
the reaction"

Note: Eyring equation in activated complex theory. k = tcYh f

d"tn R :- &LI#
for a urrimoieeular reaction
dT RT2

(ii) Use thennodynarnics aspects of Activated complex theory, to show Arrhenius

constant A for a unimoiecular reaction is given by the equation below'

k.T a's
,4: Ke i e- o ,--,-'
h
(iii)The pre-exponential factor and activaiion energy for the unimolecular reaction are

4.0 x 1013 s-l and 272kJ rnol-[, respeetivel)'' Calculate the values of A#H, A#S and A#G
for the reaction as 300 Id. State any assumption made in 5'sll. calculat :
(40 marks)

(b) (i) Write down assumption takerr in the Lindernann hypothesis for unimolecular
reactions.

(ii) Sho.n, that the unimolecular rute constant accotdrng to the Lindemairn theory is given
by the folloir,ing equation. Identify each of the rate constants, Biven in the equation
*'riting the meehanism propose<l in Lindemann Frypcr&resis. - i\. 1
k, k,lA1 o i- rr
' 1

kuni k-rlAl + k2
(iii)Another variation on the Lindemam inechanisrn involves the fonnation of an
exciplex, an excited complex-, r,vhich then goes on to react as given beiorv.
k1'
A+A ------------> A2. .S-r tr
k_1'

. k.'
'* A+F
h,
Derive a rate law f,or this mechanism and show that r-urimoiecular rate constant is
given by the following equation. Fs
,.r _ kikilAl
1-
Kuni-
{_,+kt
Is this mechanism consistent with experimental observations of the kinetics of gas-
phase unimolecutrar reactions? (40 marks)

&r \
T
 PART B
(3) (a) Internal energy is a state function andit is also considered a mechanical property.
According to the Gibbs postulate, the internal energy is equal to the average ensemble
energy in a canonical ensemble and given by
E(fi) = ------------ (i)
iZr,exp(-BE;)
where $ is the canonicll partition function, E; is the energy of the ith level and p - LlkT.

(i) Define (or explain) the following terms. (15 marks)

(rx)Intemal Energv
(B) State function (give some more examples)
(y) Ensemble
(5) Canonical ensemble
(p) Fartition function

(ii) State an equation for average of the intemal energy in a canonical ensemble in
terms of energy of the ith energy level (E1) and the probability of locating aparticle at
the ith energy level (P;). (05 marks)

(iii) Prove that fl(I) : kTz

*r" E

using the equation 1. (15 marks)

(i.i) Moleouiar partition function for translational motion is Q = TZIY)=/'v

rvhere is the rnass of the molecule and V is volume of the box. Show that average
n^r

internal energy E :1kT (10 marks)

(v) Estirnate the mean thermal velocity or"Ar in the vapour state at 700C using the
formula derived in part iv. The relative atcmic mass of iodine is 39 .95 . ( 1 0 marks)

(b) Boltzmann prohability distribution is g:ven by,pt = 1 .*p(-#)

(i) Define each tenn shor,vn in this expression (05 marks)
(ii) Find an expression for the population ratio betr,veen ith and jtl'energy level (n1lni)"
(05 marks)
io
(iii)'Ihe gy of Li is 5 13 "3 kJ mol-l. Estimate what proportion of lithium
0C..
atorns y"ionized in the atmosphere of a star at 620A
(10 marks)
(iv).V/hat is tire ten"lperature of a two-level systern of energ equivalent to
450 em-1 r,vhren the popuiation of the upper state is one lower state.
(10 rnarks)

. ACF
t(-
1"
A
(c) Ludwig Boltzmann has given a statistical view for the entropy based on the following
formula
: krnw s
(D Explain what is meant by the term W (05 marks)
(iD According to the above formula, what would be the value of entropy at 0 K? Explain.
(05 marks)
(iii) Consider a system with 10 particles having only 4 energy levels and its dominating
configuration is {4,3,2,1}. Determine the entropy of the system. (05 marks)

to

Part C
(4) (a) (i) The Coulomb's lau,can be w'ritten for the interactive force betr,veen two charges
two charges fq and 1in vacuum as below.

q2
D
qtt€a
rz

Modify the above expression for the force of attraclion (F') when the tr.vo ions are
in a solvent (10 marks)

(ii) "Water is a better solvent to dissolve ionic saits over nonpolar organic sol.,rents"

Explain this statement. (use suitableexpressions) (10 marks)

(iii) Define what is knou'n as "hydration number". (05 malks)

3-
(iv) Consider the trvo ions Br- and PO,1 Which would have,

(cr) a larger entroplr in solution

(p) a higher heat of hydration, explain briefly. (15 rnarks)

(b) (i) Electrolye solutions depart from ideality. Show that the departure from ideality for
a solution containing ion i, is proportional to its actir.'ity coetficient y1
(10 marks)

(ii) Alclj --* Alrt + 3Cl-

For the above dissociation show that

p- po + 4RT ln y+ (10 marks)

(iii) The Debye- Huckel limiting Law can be expressed as below

logy+:- Z,Z-JAli)
(o) Write an expression for l and define the terms
 (B) Calculate the mean activity coeftjcients for 0.01 M LiCl and 0.01 M CaClz
solutions. ( A: 0.509 at25o C)

(y) Calculate the electrical w-ork of charging for the both 25 0C. Explain the
reasons for the difference in the trvo values.

(6) Sketch thc Debye-Huckel plots for LiCl, CaCl2 and MgSO+ on the same axes.

(35 marks)

(c) (i) Compare between Faradaic and Non Faradaic processes. (05 marks)

(ii) Bdefly discuss how the Stem's Model could overcome some weaknesses of
Helmholtz and Gouy-Chapman Models (10 marks)

(iii) The Cornposite capacitance in the interface can be given b-v

111
C6 Cs
-: Ccc

Briefly comment on the role of Cr3 and C66 on the value of Co. (I 0 marks)

(5) (a) (i) A one step one electron process is given belou'

O+e .. R

The forward and backward rate constants for the two processes are kr and k6.
The initial concentrations of O and R are Cs and Cn. From the Butler -
volmer model of electrode kinetics following expressions can be derived,

i = nF A lk, C orr,r, - ko C^ to,rt l

kr = ko expl-x f (E - Eo)1
k6= ko expl(L-x)f (E - Eo)1
(D Define the terms appearing in the equations (08 marks)
(ii) Derive the "Butler-Volmer Formulation" of electrode kinetics using above
expressions" (12 marks)
(iii) Briefly explain the significance of k0, (15 marks)
(iv) '[he Butler -Volmer equation may be simplified when q is small as given
below,
i: - iofn
(u) Define the terms appearing
(B) Derive an expression fbr the charge transfer resistance R.,1 using the above
expression (15 marks)

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