Chem2460 2010

The University of the West Indies Course Code CHEM 2460 (C20F) 2011/Sem II
DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Senior Assistant Registrar (Examinations). The
EXTERNAL EXAMINER is requested to sign the question paper and return it with comments, if any (on a separate sheet), to
the Senior Assistant Registrar (Examinations).

..
First Examiner University Examiner

.. .
Second Examiner External Examiner (where applicable)

Date: 2011/../.. Date: 2011/../..
THE UNIVERSITY OF THE WEST INDIES
ST. AUGUSTINE

EXAMINATIONS OF APRIL/MAY 20117

Code and Name of Course CHEM 2460 (C20F) PRINCIPLES OF CHEMICAL ANALYSIS

Date and Time: Duration: TWO (2) HOURS

INSTRUCTIONS TO CANDIDATES: This paper has ELEVEN (11) pages and EIGHT (8) questions.

Answer FOUR (4) Questions, ONE (1) from EACH Section

Answer each question in a separate booklet

The use of non-programmable calculators with statistical functions is allowed.

Graph Paper to be provided.

Statistical Tables are provided.

PLEASE TURN TO THE NEXT PAGE
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SECTION A

1. As a new Teaching Assistant, one of your duties is marking first year laboratory reports. This particular
lab involves the determination of the acid content of vinegar, and then determining whether or not the
vinegar meets the manufacturers specification of 5% ethanoic acid by weight. You have just begun to
grade the results and discussion section, and find the following data presented by the student.

RESULTS
Titration of 10 mL of undiluted vinegar against 0.25 M NaOH solution.

Titration Number 1 2 3
4
Final reading, mL 30.4 36.7 42.4
32.8
Initial reading, mL 0.0 5.2 10.4 1.2
Volume base used, mL 30.4 30.5 32.0 31.6

31.125 0.80 mL NaOH used to neutralize 10 mL undiluted vinegar

Concentration of vinegar = 0.778 0.020 M (5% vinegar is equivalent to 0.833 M)

CALCULATIONS
Using a single-sided t-test, I make the following hypotheses:
H
0
: There is a significant difference between the measured and theoretical [CH
3
COOH] in the vinegar.
H
A
: There is no significant difference between the measured and theoretical [CH
3
COOH] in the vinegar.

From single-sided t-table @ 95% confidence: t-crit = 2.132
Therefore, t-calc < t-crit. I accept the null hypothesis.

DISCUSSION
Using a single-sided Students t-test at 95% confidence, I conclude that the vinegar does not
meet the manufacturers specifications of 5% ethanoic acid because there is a significant
difference between the measured [CH
3
COOH] and the theoretical [CH
3
COOH] (t-calc < t-crit).
The concentration of ethanoic acid in the vinegar is less than the theoretical value.
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Question 1 continued.
Grading Scheme:
Criteria F D C B A
Number of errors > 8 7 8 5 6 3 4 1 2
Use the grading scheme above to decide on a grade for this students lab, clearly pointing out all errors
and the effect these errors would have on the validity of the experimental results. In addition, provide
feedback to the student, supplying the correct answers where necessary as well as explaining the basis of
any errors, important omissions or misconceptions. [25 marks]

2. An experiment was conducted to see if microorganisms grown under various conditions would produce
surfactants, chemicals that would reduce the surface tension of seawater. This was done by growing
bacteria in seawater containing different organic chemicals and then comparing those surface tensions to
that of plain seawater. The following table provides the results of the experiment.

Table 1. Results of the surface tension experiment. Results are provided as
mean one standard deviation, with n = 4 for all experiments.
Type of medium Surface tension (dynes/cm)
Plain seawater 65.2 1.94
Phenanthrene + seawater 59.7 3.02
Fluoranthene + seawater 64.8 0.67

Which, if any, of the seawater media resulted in the production of surfactants? Be sure to fully explain
your conclusion, clearly showing complete statistical analyses to support your conclusion.
[25 marks]

END OF SECTION A

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SECTION B

3. Phosphate may be determined in a soil sample as follows:
1. Weigh 0.5g finely ground soil sample into a boiling tube
2. Add 5mL concentrated nitric acid and reflux at 130
o
C for 6 hours
3. Dilute the sample with 5mL distilled water and filter through Whatman #542 filter paper into a
50mL volumetric flask; make to volume with distilled water rinses of the sample tube and filter
4. Pipette 5mL of sample extract into a test tube
5. Add 0.8mL of a mixed molybdate reagent and allow the characteristic blue colour to develop over
1 hour
6. Measure the sample absorbance at 830nm
7. Using a range of phosphate standard solutions similarly prepared, determine the phosphate
concentration in the soil sample
(a) Explain how (i) the Detection Limit and (ii) the Limit of Quantitation may be determined for the
above procedure, using appropriate equations to illustrate your answer. [10 marks]
(b) Identify where errors can be made in the above procedure and describe the measures that you would
take, to ensure that the highest levels of accuracy of analysis are obtained. [15 marks]


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4. Assume that you are required to undertake a study of sodium benzoate in a range of preserved fruits
commonly consumed by children. The maximum permissible level (MPL) of sodium benzoate in
preserves is 0.1% by weight. If the study is to be completed in 3 months and must operate within a
specified budget, discuss the criteria that should be met by the test method, to ensure that:
(a) The project can be completed within the time frame and budget.
(b) The highest accuracy and precision of test results are obtained, to allow recommendations for action
on samples exceeding the MPL. [25 marks]

END OF SECTION B

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SECTION C

5. In the year 2020, a nuclear reactor on the Gulf of Paria near San Fernando, Trinidad, is struck by a
tsunami. It is destroyed, fires break out, and there is likely contamination of the air, water and soil. The
tsunami has also overwhelmed the petroleum and chemical industries near Point Lisa. The stunned
citizens are concerned about effects of the disaster on the air, water, soil, crops, fish and wildlife and
human health. You are assigned to develop a monitoring plan to determine the extent of contamination.
Make sure your plan specifies all of the necessary equipment (including safety equipment),
decontamination/cleaning procedures, preservation, holding times and Quality Assurance/Quality Control
(QA/QC) protocols. Potential significant pollutants involve radioactive aerosol (atmospheric particulate
matter) and gases from the burning nuclear reactor, plus ammonia and methanol from the chemical
industries. The petroleum industry has also been affected, with releases of volatile and semivolatile
organic compounds into the air and liquid petroleum releases into the Gulf of Paria and into the soil.

Since in 2020 Trinidad & Tobago is a developed country, and the wise government has saved money for
such possible disasters, you have available any equipment and resources you need to determine the extent
of the disaster. [25 marks]


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6. Answer, in detail, the following questions. Please give specific examples and draw diagrams as
appropriate to illustrate your answer.
(a) What are some of the commonly analyzed substances or parameters in water samples and how are
they measured? Which are best measured in the field, and why? [5 marks]
(b) What is the purpose of a chain-of-custody form? What is holding time? Describe methods of
proper sample preservation and storage and give examples. [5 marks]
(c) Define the different types of blanks, and give the purpose of each. Define spikes and duplicates, and
describe their purpose. [5 marks]
(d) What is a sample matrix? What are the principal ways and means of dissolving inorganic
materials? What is a flux? When is it used? [5 marks]
(e) Differentiate between wet ashing and dry ashing. Describe the principles of dry ashing and wet
digestion of organic and biological materials. List the advantages and disadvantages of each.
[5 marks]

END OF SECTION C

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SECTION D

7. (a) The equation for the standard addition method assuming that concentration is directly proportional to
the instrument response is given by:

(i) Modify Equation 1 for an analysis involving UV/VIS spectroscopy assuming that the chemical
system follows Beers law. [2 marks]
(ii) Derive the equations for a UV/VIS analysis using the standard addition method and ONLY
TWO increments of sample. Show how you will obtain c
x
from these equations.
[3 marks]
(iii) A 2.00 mL urine sample was analysed for phosphate using the molybdenum blue method
absorbing at 820 nm. After the derivatization, the sample was diluted to 100.00 mL in a
volumetric flask. Phosphate was determined in the diluted solution as follows:
Volume of Sample
taken (mL)
Volume of 0.050
mgmL
-1
std. phosphate
solution added (mL)
Volume of H
2
O
added (mL)
Absorbance at 820
nm in a 1.0 cm cell
25.0 0.0 1.0 0.428
25.0 1.0 0.0 0.517

Calculate the concentration of phosphate in mgmL
-1
in the original urine sample.
[5 marks]
(b) A series of permanganate solutions of varying concentrations were used to prepare a calibration
curve as shown in Table 1. The absorbances were recorded at 525 nm in 1.0 cm cells.
TABLE 1
/ M 30.00 60.0 90.0 120.0 150.0
A
525
0.160 0.330 0.490 0.660 0.840

(i) Plot a calibration curve from the data in Table 1. [10 marks]
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Question 7 continued.
(ii) Determine the concentration of [MnO
4
] in M of an unknown sample which gave an

absorbance of 0.540 using your calibration curve in [b (i)]. [2 marks]
(iii) Determine the molar absorptivity of the [MnO
4
] solution at 525 nm. [3 marks]

8. (a) Titanium and vanadium can be measured simultaneously as their peroxide complexes. The molar
absorptivities of titanium and vanadium peroxide complexes at 400 and 460 nm are as follows:
400 nm 460 nm
c
Ti
644

321

c
V
145

232

A steel sample was dissolved, treated with H
2
O
2
and absorbances measured at 400 and 460 nm were
0.172 and 0.116, respectively, in a 1.0 cm cell. Calculate the concentration of Ti and V in the steel
sample. [10 marks]
(b) The sodium salt of 2-quinizarinsulfonic acid (NaQ) forms a complex with Al
3+
that absorbs at 560
nm.
(i) Use the data in the following table and a suitable graphical plot to determine the formula of
the complex given that the concentration of Al
3+
in all solutions was 3.7 10
-5
M and
absorbance was recorded using a 10 mm cell.
C
NaQ
(M) A
560

C
NaQ
(M) A
560
1.00 10
-5
0.13

5.00 10
-5
0.49
2.00 10
-5
0.27

6.00 10
-5
0.50
3.00 10
-5
0.40

8.00 10
-5
0.50
4.00 10
-5
0.47

1.00 10
-4
0.50
(ii) Find the molar absorptivity of the complex. [15 marks]
END OF SECTION D
END OF EXAMINATION PAPER
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REFERENCE MATERIAL

Equations
=
i
i
n
x
x
) 1 (
) (
2

=
n
x x
s
i
i
Variance = s
2
100 = =
x
s
CV RSD
n
o
= (s.e.m.) mean the of error standard
2
2
smaller
larger
s
s
F =
|
|
.
|
\
|
=
n
s
t x n small for limits Confidence
( )
s
x n
t

=
2 1
2 1
1 1
n n
s
x x
t
p
+
=
( ) ( )
) 2 (
1 1
2 1
2
2 2
2
1 1 2
+
+
=
n n
s n s n
s
p

2 . .
2 1
+ = n n f d
2
2
2
1
2
1
2 1
n
s
n
s
x x
t
+
=
( ) ( )
|
|
.
|
\
|
|
|
.
|
\
|
+
=
1 1
. .
2
2
2
4
2
1
2
1
4
1
2
2
2
2
1
2
1
n n
s
n n
s
n
s
n
s
f d

Tables
Table 1. t-values for double-sided (top) and single-sided (bottom) tests.
t - tables : double-sided tests
d.f. 0.100 0.050 0.020 0.010 d.f.
1 6.314 12.706 31.821 63.656 1
2 2.920 4.303 6.965 9.925 2
3 2.353 3.182 4.541 5.841 3
4 2.132 2.776 3.747 4.604 4
5 2.015 2.571 3.365 4.032 5
6 1.943 2.447 3.143 3.707 6
7 1.895 2.365 2.998 3.499 7
8 1.860 2.306 2.896 3.355 8
9 1.833 2.262 2.821 3.250 9
10 1.812 2.228 2.764 3.169 10
11 1.796 2.201 2.718 3.106 11
12 1.782 2.179 2.681 3.055 12
13 1.771 2.160 2.650 3.012 13
14 1.761 2.145 2.624 2.977 14
15 1.753 2.131 2.602 2.947 15
20 1.725 2.086 2.528 2.845 20
d.f. 0.050 0.025 0.010 0.005 d.f.
t - tables : single-sided tests

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Table 2. Critical values for a single-sided F-test at p = 0.05 (generated using the FINV function on MS Excel)

Degrees of freedom of the NUMERATOR

2 3 4 5 6 7 8 9 10 11 12 13 14 15
D
e
g
r
e
e
s

o
f

f
r
e
e
d
o
m

o
f

t
h
e

D
E
N
O
M
I
N
A
T
O
R

2 19.00 19.16 19.25 19.30 19.33 19.35 19.37 19.38 19.40 19.40 19.41 19.42 19.42 19.43
3 9.55 9.28 9.12 9.01 8.94 8.89 8.85 8.81 8.79 8.76 8.74 8.73 8.71 8.70
4 6.94 6.59 6.39 6.26 6.16 6.09 6.04 6.00 5.96 5.94 5.91 5.89 5.87 5.86
5 5.79 5.41 5.19 5.05 4.95 4.88 4.82 4.77 4.74 4.70 4.68 4.66 4.64 4.62
6 5.14 4.76 4.53 4.39 4.28 4.21 4.15 4.10 4.06 4.03 4.00 3.98 3.96 3.94
7 4.74 4.35 4.12 3.97 3.87 3.79 3.73 3.68 3.64 3.60 3.57 3.55 3.53 3.51
8 4.46 4.07 3.84 3.69 3.58 3.50 3.44 3.39 3.35 3.31 3.28 3.26 3.24 3.22
9 4.26 3.86 3.63 3.48 3.37 3.29 3.23 3.18 3.14 3.10 3.07 3.05 3.03 3.01
10 4.10 3.71 3.48 3.33 3.22 3.14 3.07 3.02 2.98 2.94 2.91 2.89 2.86 2.85
11 3.98 3.59 3.36 3.20 3.09 3.01 2.95 2.90 2.85 2.82 2.79 2.76 2.74 2.72
12 3.89 3.49 3.26 3.11 3.00 2.91 2.85 2.80 2.75 2.72 2.69 2.66 2.64 2.62
13 3.81 3.41 3.18 3.03 2.92 2.83 2.77 2.71 2.67 2.63 2.60 2.58 2.55 2.53
14 3.74 3.34 3.11 2.96 2.85 2.76 2.70 2.65 2.60 2.57 2.53 2.51 2.48 2.46
15 3.68 3.29 3.06 2.90 2.79 2.71 2.64 2.59 2.54 2.51 2.48 2.45 2.42 2.40

Table 3. Critical values for a double-sided F-test at p = 0.05 (generated using the FINV function on MS Excel)

Degrees of freedom of the NUMERATOR

2 3 4 5 6 7 8 9 10 11 12 13 14 15
D
e
g
r
e
e
s

o
f

f
r
e
e
d
o
m

o
f

t
h
e

D
E
N
O
M
I
N
A
T
O
R

2 39.00 39.17 39.25 39.30 39.33 39.36 39.37 39.39 39.40 39.41 39.41 39.42 39.43 39.43
3 16.04 15.44 15.10 14.88 14.73 14.62 14.54 14.47 14.42 14.37 14.34 14.30 14.28 14.25
4 10.65 9.98 9.60 9.36 9.20 9.07 8.98 8.90 8.84 8.79 8.75 8.71 8.68 8.66
5 8.43 7.76 7.39 7.15 6.98 6.85 6.76 6.68 6.62 6.57 6.52 6.49 6.46 6.43
6 7.26 6.60 6.23 5.99 5.82 5.70 5.60 5.52 5.46 5.41 5.37 5.33 5.30 5.27
7 6.54 5.89 5.52 5.29 5.12 4.99 4.90 4.82 4.76 4.71 4.67 4.63 4.60 4.57
8 6.06 5.42 5.05 4.82 4.65 4.53 4.43 4.36 4.30 4.24 4.20 4.16 4.13 4.10
9 5.71 5.08 4.72 4.48 4.32 4.20 4.10 4.03 3.96 3.91 3.87 3.83 3.80 3.77
10 5.46 4.83 4.47 4.24 4.07 3.95 3.85 3.78 3.72 3.66 3.62 3.58 3.55 3.52
11 5.26 4.63 4.28 4.04 3.88 3.76 3.66 3.59 3.53 3.47 3.43 3.39 3.36 3.33
12 5.10 4.47 4.12 3.89 3.73 3.61 3.51 3.44 3.37 3.32 3.28 3.24 3.21 3.18
13 4.97 4.35 4.00 3.77 3.60 3.48 3.39 3.31 3.25 3.20 3.15 3.12 3.08 3.05
14 4.86 4.24 3.89 3.66 3.50 3.38 3.29 3.21 3.15 3.09 3.05 3.01 2.98 2.95
15 4.77 4.15 3.80 3.58 3.41 3.29 3.20 3.12 3.06 3.01 2.96 2.92 2.89 2.86

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The University of the West Indies Course Code CHEM 2460 (C20F) 2011/Sem II

] in M of an unknown sample which gave an

] solution at 525 nm. [3 marks]

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