THIS IS A SAMPLE FINAL EXAM-The exam you will be tested on may be somewhat

different!
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CHEM1313 Final Exam 04/26/04
Spring 2004
This exam consists of six (6) questions. Points awarded for each question are indicated after
each part. Only a calculator and a pen/pencil are allowed for this exam. Sheets with potentially
useful equations, tables, and constants are included as the final pages of this exam. Make sure
you read each question carefully. Use the back side of the page if needed.
1) In many European countries pollution caused by automobiles is monitored by measuring the
heavy metal content in plant tissues. In a comparison of two methods for the determination of Cr
in rye grass, the following results were obtained (expressed as ppm Cr):
Method 1: 3.21, 3.17, 3.05, 3.61, 3.33
Method 2: 3.10, 3.01, 2.97, 2.90, 2.95
a) Are there any outliers in the first data set at the 95%confidence level? (5 points)
b) Calculate the 95% confidence limit for the mean Cr content reported by Method 1. Use the
standard deviation to estimate the precision of this Method. (5 points)
c) Are the results reported by both methods different at the 90% confidence level? (10 points)

Problem 2)
12 ml of a 0.1 M H2A solution are titrated with 0.15 M KOH (KOH is the titrant). The acid
dissociation constants for H2A are Ka1=6.9 x 10-6 and Ka2=4.3 x 10-10 respectively.
a) Calculate the volume of KOH necessary to reach the first and second equivalence points. (5
points)
b) Qualitatively draw the titration curve. Mark on the plot the most important points. Indicate in
the plot the volume of KOH needed to reach the first two buffer regions and their approximate
pH. (10 points)
c) Write a mass balance for H2A and the charge balance for the solution. (5 points)
d) Calculate the pH of the solution that would result from the addition of 5 ml of KOH to the
H2A solution described above. (5 points)
e) Calculate the approximate pH of the second equivalence point (10 points). Verify if your
approximations are valid, and explain how you would obtain a more accurate value.

3)
a) (15 points). If the solubility-product constant for AgBr (s) is 5x10-13 and the standard
potential (vs. SHE) for the reduction of Ag(I) to Ag(0) is:
Ag + ( aq ) + e
Ag 0 ( s )
E0=0.799 V
If the solution is in equilibrium, calculate E0 for the following reaction :
AgBr ( s ) + e
Ag 0 ( s ) + Br ( aq )
b) (5 points). Calculate the potential (vs. SHE) of a half cell consisting of a Cu0 electrode
immersed in a solution saturated in Cu2S.
(E0Cu+/Cu0 = 0.521 V, Ksp(Cu2S)=2.5x10-48)
Hints: First write mass balances for Cu+and S-2 expressing them as a function of the
molar solubility. (Pay attention to the oxidation state of Cu in this half reaction!).

4) 25 ml of a 0.05 M H2S solution are titrated with 0.1 M NaOH (NaOH is the titrant). The acid
dissociation constants for H2S are Ka1=9.6 x 10-8 and Ka2=1.3 x 10-14 respectively.
a) Calculate the volume of NaOH necessary to reach the first and second equivalence points. (2
points)
b) Draw the titration curve. Indicate in the plot the volume of NaOH needed to reach the first two
buffer regions and their approximate pH. (3points)
c) Write a mass balance for H2S and the charge balance. (5 points)
d) Calculate the pH of the solution that results from the addition of 5.8 ml of NaOH to the H2S
solution described above. (5 points)

5) Draw a block diagram of the instrumental setup for the following UV-Vis spectrophotometer
configurations (include the radiation source, monochromator, sample holder(s) and detector):
a) Single beam spectrophotometer. (2 points)
b) Dual-beam-in-space spectrophotometer. (1 point)
c) Dual-beam-in-time spectrophotometer. (2 points)
d) Briefly mention two advantages of dual-beam spectrophotometers when compared to single
beam instruments. (5 points)

6) The half reaction occurring in the calomel reference electrode is:

Hg 2 Cl 2 ( s ) + 2e
2 Hg (l ) + 2Cl
E0=0.268 V
a) Identify the oxidation state of all the Hg species. (1 point)
b) Write the Nernst equation for this half reaction. (2 points)
c) Make a drawing of the reference electrode. (3 points)
d) Calculate the potential of the following electrochemical cell: (6 points)
Zn 0 Zn( NO3 ) 2 (0.03M ) Hg 2 Cl 2 ( s ), KCl (4.6M ) Hg 0
E0(Zn+2/Zn0)= -0.763 V
e) Is the reaction of the electrochemical cell described above spontaneous? (3 points)

Statistical Tables and Equations:

Critical Values of Q

N
3
4
5
6
7
8
9
10

90%
0.941
0.765
0.642
0.560
0.507
0.468
0.437
0.412

s=

95%
0.970
0.829
0.710
0.625
0.568
0.526
0.493
0.466

Critical Values of t
Degrees of
Freedom 80%
3.08
1
1.89
2
1.64
3
1.53
4
1.48
5
1.44
6
1.42
7
1.40
8
1.38
9
1.37
10
1.36
11
1.36
12
1.35
13
1.34
14
1.29
infinity

99%
0.994
0.926
0.821
0.740
0.680
0.634
0.598
0.568

Qcalc =

(x x )
i =1

Level of Confidence
90% 95% 99% 99.90%
6.31 12.70 63.70 637.0
2.92
4.30
9.92 31.60
2.35
3.18
5.84 12.90
2.13
2.78
4.60
8.60
2.02
2.57
4.03
6.86
1.94
2.45
3.71
5.96
1.90
2.36
3.50
5.40
1.86
2.31
3.36
5.04
1.83
2.26
3.25
4.78
1.81
2.23
3.17
4.59
1.80
2.20
3.11
4.44
1.78
2.18
3.06
4.32
1.77
2.16
3.01
4.22
1.76
2.14
2.98
4.14
1.64
1.96
2.58
3.29

d
range

Beers Law: A = b c

N 1

Single point standard addition

xa xb

texp =

s pooled

s pooled =

Ax = b c x

N a + Nb
N a Nb

As = b

(c x V x + c s V s )
Vt

Nernst Equation:
ne
Given aA + bB
cC + dD
0.0592
[C ]c [ D ]d
E = E0
log
n
[ A]a [ B ]b

sa2 ( N a 1) + sb2 ( N b 1)
Na + Nb 2

CL for = x t

Vx
Vt

s
Henderson-Hasselbalch equation:
c
pH = pK a + log acid
cbase