UNIVERSITY OF SWAZILAND

SUPPLEMENTARY EXAMINATION 2014/2015

TITLE OF PAPER . Advanced Analytical Chemistry

COURSE CODE C404

TIME ALLOWED Three (3) Hours.

INSTRUCTIONS Answer any Four (4) Questions. Each

Question Carries 25 Marks

A periodic table and other useful data have been provided with this paper.

REQUIREMENT: GRAPH PAER

DO NOT OPEN TmS QUESTION PAPER UNTIL PERMISSION TO DO SO

HAS BEEN GRANTED BY THE CHIEF lNVlGILATOR.

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Question 1 (25 marks)

(a) What are the factors that influence the conductivity ofan electrolyte? From the list of
stated facto~ identify the most important one and state the factors that affect its own
value too. [5]

(P) (i) Define the terms 'cell constant' and 'equivalent conductance'
(ii) State their respective S.1. units and obtain an expression that relates the two'
[5]
(c) Using the pmciples of ionic atmosphere, discuss (with an illustrative example), the
variation of limiting ionic conductance, A°+, ofcations ofelements in the same group of
the periodic table. [5]
(d) A 560.75mg weak, monobasic acid, HB, (F.W. 122), was dissolved in 250 mL of
dionized water at 25°C. Ifthe measured resistance of the solution is 5570 at 25°C, and
the cell constant ofthe conductivity cell is 0.075 cm-1, calculate the following for
the acid: ,.
(i) The molar conductance.
(ii) The degree ofdissociation.
(iii) The ionization constant. 10]
(Ao H ... =349.6,Scm mor\ A~ = 40.9Scm mor
3 3 1
)

Question 2 (25 marks)

(a) State the precautionary steps you would take in order to maximize accuracy of data
during a conductometric titration [4]

(b) Summarize the general procedure for end point determination during a conductometric
titration. Why are measurements near the equivalent point unnecessary? [3]

(c) With specific examples and illustrative diagrams, explain why the titration ofa weak acid
with a weak base is preferred to the titration ofa weak acid with a strong base. [4]

(d) Show the general forms of the titration curves for the following conductometric titrations
and indicate the equivalent point in each case;
(i) Titration ofHCl solution with 0.50M NaOH.
(ii) Titration ofHCI solution with 0.50MNH.tOH [4]

 (e) A solution containing a mixture ofan aliphatic acid and an aromatic sulphonic acid was
titrated conductometrically with a 0.200MNH3 solution (as titrant). The conductance data
obtained (after correction for the titrant volume) are as follows:

Burette 0.00 1.00 2.00 2.50 30.. 3.20 3.50 4.20 4.50 5.00 6.00 8.00
Reading\mL
NS cmlequiv- l 2.01 1.75 1.47 1.33 1.19 1.19 1.26 1.47 1.51 1.51 1.52 1.53

(i) Determine the number of equivalents ofeach acid present in the mixture.
(n) Comment briefly on the shape ofthe titration curve. [10]

Question 3 (25 marks)

(a). Enummerate the salient properties of an ideal reference electrode? [4]

(b). For the AgiAgCI reference electrode:

(n) Write the half-cell reaction and its shorthand notation. [2]
(ii) Write the Nernst equation for its potential and show that the potential depends
on the [KCI], the filling solution. [3]
(iii). Draw a labeled schematic diagram of this electrode and briefly describe its
preparation. [5]
(iii) Give one advantage and one disadvantage ofthis electrode when compared
with the saturated calomel electrode (SCE). [2]
(iv) Which is more temperature dependent - the one prepared using saturated KCl
or the one prepared using 3.5M KCI? Explain. [4]

©. A cell was prepared by dipping aPt wire(indicator electrode), and a S.C.E into a solution
containing a 02M Fe3+ and O.lM Fe2+ and the two were connected to a potentiometer so that
the Pt-wire is the cathode while the S.C.E is the anode.
Calculate the theoretical cell voltage, given that:

Fe3+ + e" = Fe2+ : EO = +O.771V

Erer = 0.245V(i.e. Esce = 0.245V)

Eg = 0, and Activity Coefficient = 1.0 [5]

3
 Question 4 (25 marks)

(a) Summarize the make up, the half - cell line notation and the half cell reaction of a
saturated calomel electrode. [6]

(b). The potential (in volts), of some reference electrodes vs SHE, as a function of
temperature are as tabulated below:

AglAgCI
I Temp(°C) Calomel(O.lMKU) Calomel(Saturated KCL)
(Saturated KCI)

10 0.3362 0.2543 0.2138

20 0.3359 0.2479 0.2040
25 0.3356 0.2444 0.1989
30 0.3351 0.2411 " 0.1939
40 0.3336 02340 0.1835

(i) Identify the electrodes having the poorest potential stability qith temperature variation.
How does this observation affect its performance as a reference electrode? [4]
(ii) Arrange the electrodes in the increasing order oftheir potential- temperature
coefficient(or gradient). [2]
(iii) Which would you prefer for an analysis: a saturated calomel electrode or a O.IM
KCI calomel electrode? Why? [3]

(c) what are the advantages ofAgjAgCI reference electrode over a SCE [2]

(d) A cell consisting of a SCE (E = 0.25V), and an electrode ofunknown potential, has a cell
potential of 0.62 V. Calculate the potential ofthe unknown electrode if
the polarity ofthe SCE is: (i) positive, (ii) Negative
[8]

Question 5 (25 marks)

(a) Give a classification of ion selective electrodes and give aD. example in each case.[6]

(b) State three favourable features of ion selective electrodes. [3]

4
(c) In general, W ions interfere during the use of other types of glass membrane electrodes.
Suggest bow serious W ion interference can be avoided during the analysis of other
cations using a glass membrane electrode. [2]

(d) (i~ using appropriate d.ia.gratns, descn"be the make up~ the working mechanis~ the
electrode response and the major interfering ion of a fluoride ISE. [6]
(ii) To which class ofthe ISE does it belong? [1]
(iii) W hy is the membrane ofthis electrode is dopped with Eu(II). [2]

(e) A lithium ion - selective electrode bas a selectivity coefficient, Ku +. 00+ = 5.0 x 10-5• On
being laced in a 3.44 x 104 M Lt solution, its potential, v~us SeE, was -0.333V.
ea
Calculate its potential when 2+ is added to give 0.100 M Ca2+. [5]

Question 6 (25 marks)

(a) State the differencels between

(i) Voltammetry and potentiometry,
(ii) Voltammetry and coulometry. [4]

(b) Briefly account for the following observations:

(i) Highly reproducible current-potential data often obtained from polarographic analysis.
(ii) W reduction does not interfere with most reductions at the Hg surface of a DME.
(iii) Alkali metals (with lower standard potentials) can be reduced more easily than W at a
DME.
(iv) A DME is preferred for cathodic reactions during amperometric titrations while aPt
electrode is preferred for anodic reactions. [10]

(c) At the D~ the iodate ion undergoes the following reaction:

When a l.4lmM solution ofKIO) in a O.IM perchloric acid was

reduced polarographically at a DME with a drop time of2.18s and Hg
flow rate of 2.67mg1s, the diffusion current was 37.1 JLA.Determine the
diffusion coefficient ofthe iodate ion in O.IM perchloric acid. [11]

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178.49
Hf ..
180.95
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183.85
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186.21
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r
t~O;2, '

55 56 57 72 73 74 "" .15

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58 ' 59" :, 60'

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constant
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constant

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'--"--'--- - ------ - .--- ---_._- -_. ­
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. YOi' + 6H"" + Se-' = !1 2 + 3H 2O;" .1:2'&
Br 2(1) + 2e- .
= 2Br~ 1.065
lCli+e-'
= 112 + 2Cr­ '. 1.06:

Vor +2H++ e-
:V02+ + H 2O
= 1.00­
HNO: + H+ + e-
= NO(g) + H2O" '1.00

NOi + 3H+· + 2e­ = HN0 1 + HlO .0.94 .

2Hg2+ +2e­ == Hgi+ 0.92
.,
Cu 1 + + y- -i- e-
=; CUl(s}
0.86

Ag+ + e­ Ag
0.7"99

'H !h2+'..+.?_e ­ = ~Hg 0.79

Fe'+ :+ e- . = Fe z+ 0.771·

02(g) + 2H+ + 2e~ H 20 l 0.682

2HgCli + 2e­ = Hg 2Cl l (s) + ~Cl- . 0.63
.HgISO~(S)·:+ 2e-: . "'I' 2Hg + SO~- o.6is

SblOS + 6H+ + 4e­ .= 2SbO+ + 3H I O . . 0.581

Hl~S04 + 2H+ + 2e-. = HAsO l +2H:P 0.559

Ii +2e­ 31.- ­ 0.545
Cu+ + e­ = Cu 0.52 .
V0 2 ++ 2B+ + e- V·+ + H. 10
. 0.337
Fe{CNH- + e-
Fe(CN')~- 0.36

Cu l + +.2e­ Cu . 0.337

UOi~ + 4H+ + 2e­ U'" + 2H 2 O 0.334

(\-"olltirllled)
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" Ni:+,Sf1~ '!;"• • .

NiH f.·2L':'
", ...... :
, y3+':i-e-:: '·-Q.255
Col-> '1- 2e­ = Co ' ..... 0.277 '
Ag(CN)2" + e-
= Ag+'2CN- ,-0.3\ ,
Cd l + + 2,­ ,Cd ":'0.403.
'CrJ+ + e- Crl+ ", -OAI
Felt + 2e'­ =i Fe -0.440
2C0 2 + 2H+ + 2e- , Hl C1 0 4 "':'0.49
H 3P0 3 + 2H+ + 2e­ ,';".'HPH10 1 + H 20 -O.5Q
U 4 + Te-:
-0.6\
Z!lH +2e-,
= Zn , -0.763,
Crl+'+ 2e­ = Cr -0.91
'Mn 1 + + 2e~' ='Mn .... US
,Z,4+ + 4e:­ Zr -1.53
, TiH 4- 3e-­ Ti -1.63
AI l + 4- 3e­ AI -1.66
Th 4 + + 4e­ = Til -1,90
'Mg2+ + 2~­ Mg -2.31
La 3 + + 3e-, = La -2.52
Na+ + e­ N~ - 2.714
Ca H + 2e­
Ca -2.87 :,
Sr1+ + 2e­
Sr' -2.89.
K+ + e­
K -2.925
Li+ +'e­ Li ,-3.045

, .