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Hour Examination

HUS/Illinois Chemistry 222

May 27, 2010

This examination is made up of 4 questions. Answer the easiest question first. "How do we know
which question is easiest?" You have to read them all first, then decide!

No talking during the examination. You may have ONE sheet of paper on which you have written
whatever equations you wish. You may use a calculator. No talking during the examination. If
you talk during the exam, on the first offense, you lose 5 points. On the second offense, you lose 10
more points. If there is a third offense, your grade is a zero.

If a question is unclear, you may raise your hand and ask Prof. Scheeline to explain.

In all cases, show your work. Simple answers of "Yes, No, 17.5" will not earn points. Your reasons
and approach to solving the problems are more important than the answers themselves.

1. Statistics and Error Propagation.

Here is the output from a regression analysis in Excel.


SUMMARY OUTPUT

Regression Statistics
Multiple R 0.99985
R Square 0.9997
Adjusted R
Square 0.99964
Standard Error 0.002699
Observations 7

ANOVA
df SS MS F
Regression 1 0.121468 0.121468 16669.68
Residual 5 3.64E-05 7.29E-06
Total 6 0.121504

Standard
Coefficients Error t Stat P-value
Intercept 3.296733 0.001839 1792.354 1.03E-15
X Variable 1 0.329323 0.002551 129.1111 5.29E-10
a) From the data provided, is there any indication that the data are nonlinear? Explain your
answer. (5) Because the t statistics are large and because we have no plot of residuals, there
is no way to determine if the data are nonlinear. This does NOT prove they are linear – only
that we can't prove they aren't!

b) If the signal is current in microamperes and concentration is in ppm, then what concentration
is correlated with a signal of 4.5 microamperes? (5) S = S0 + m C.
C = (4.5-0.3)/3.3 = 4.2/3.3 = 1.27 ppm (or, given that we only have 2 significant figures,
1.3 ppm)

c) When the calibration was actually done, the highest concentration used was 1.2 ppm. How
does this affect the validity of your result in b)? (5) The answer in b) is an extrapolation, and
thus may not be reliable. Working curves should only be interpolated, not extrapolated.

d) Express the slope and intercept with the correct number of significant figures. (5) Slope =
0.329±0.003 ppm μA-1; intercept = 3.297±0.002 μA.

e) A spectrometer is set at 520 nm. Integrated over 1 s, one observes approximately 1010
photons. Ignoring all noise sources except the counting statistics of photons, what is the
signal-to-noise ratio for this measurement? (5) For countable events, S/Nmax = count1/2 = 105

2. Weak Acids/Weak Bases/Buffers. On the road between Hanoi and Hai Phong, there is a factory
that produces HCl, H3PO4, Na2HPO4, NaOH, and Cl2. Cl2 dissolved in water dissociates almost
completely into HCl and HOCl. Cl2 + H2O ↔ HCl + HOCl K~300.

a) If you have 25 mL of 0.05 M H3PO4, sketch the expected titration curve using 0.05 M NaOH,
showing pH at the beginning of the titration (3), half-way to the first equivalence point (3), at
the first equivalence point (3), half-way to the second equivalence point (3), at the second
equivalence point (3), and 5 mL past the second equivalence point (3). Use approximate
expressions where possible to make the calculations go rapidly.

b) You are worried that someone has mixed Cl2 with H3PO4. Suggest how, using titration with
NaOH and measurement of the titration curve with a pH meter, you could

i. distinguish samples of pure H3PO4 from samples of mixed HCl and H3PO4 (5)

ii. distinguish H3PO4 from samples of mixed Cl2 and H3PO4. (5)
Useful pKa values:
H3PO4:2.15, 7.20, 12.375
HOCl: 7.53

For a):

Initial pH: Ka =10-2.15 =7.08×10-3 = [H+][H2PO4-]/[H3PO4]. Assume all H+ comes from H3PO4
dissociation. 7.08×10-3 = x2/(0.05-x). Approximate x0 = 0. (7.08×10-3 (0.05))1/2 = 1.88×10-2.
(7.08×10-3 (0.05-1.88×10-2))1/2 = (7.08×10-3 (0.0312))1/2 = 1.49×10-2 M.
(7.08×10-3 (0.05-1.49×10-2))1/2 = (7.08×10-3 (0.0351))1/2 = 1.58×10-2 M.
(7.08×10-3 (0.05-1.58×10-3))1/2 = (7.08×10-3 (0.0342))1/2 = 1.56×10-2 M.
Good to better than 3%, so stop. pH = -log10(0.0156 M) = 1.81
Half-way to first equivalence point, pH = pK1 = 2.15
First equivalence point is an ampholyte so pH = (pK1+pK2)/2 = (2.15+7.2)/2 = 9.35/2 = 4.68.
Half-way to second equivalence point, pH = pK2 = 7.2.

Second equivalence point is an ampholyte so pH = (pK2+pK3)/2 = (7.2 + 12.375)/2 = 19.575/2 =


9.79.
5 mL past the second equivalence point, Ka3 = [H+](0.2 C0)/(0.8 C0) so 10-12.15 = x/4. x = 4*10-12.15
= 2.8×10-12 M. pH = -log10(2.8×10-12) = 11.55.
b) i) The HCl is a strong acid, so it will be completely titrated before the H3PO4 first proton is
titrated. Thus, the volume to go from the initial pH to the first equivalence point will be
GREATER than the volume needed to go from the first equivalence point to the second
equivalence point.
ii) This is actually harder. The pKa of HOCl is nearly the same as the pKa of the second proton in
H3PO4. The proton from HCl will titrate in parallel with the first phosphoric acid proton. Thus,
the volumes for both steps of the titration will be equal. Indications of a problem might show up
as a small shift in pH at the mid-point of the titration buffer regions. Probably the best way to
detect if there is a problem is to find a reactant that consumes HOCl but not phosphoric acid. For
example, Cl2 + alkenes give dichloro alkanes. HOCl + reducing agent produces Cl-. If titration
after addition of a reductant gives the same result as with the reductant, then there is probably no
HOCl present. A complication, however, is that reductants may influence pH. For example,
2Fe2+ + HOCl →2 Fe3+ + Cl- + OH-. On the other hand, this will influence the titrant volume
required to get to the first equivalence point, and that's how the influence of HOCl can be altered.

3. Spectrophotometry. This question is based on K. Morita and E. Kaniko, "Spectrophotometric


Determination of Arsenic in Water Samples Based on Micro Particle Formation of Ethyl Violet-
Molybdoarsenate," Anal. Sci. 22(8), 1085-1089 (2006)
[http://www.jstage.jst.go.jp/article/analsci/22/8/22_1085/_article]. AsO33- is oxidized to AsO43-
by KIO3 so the assay looks at TOTAL arsenic as arsenate. The reaction is:
H3AsO4 +molybdate → AsMo12O403-
3 Ethyl Violet + AsMo12O403- → (EV)3AsMo12O40 blue, aggregate complex, absorption
maximum 612 nm.
The complex follows Beer's Law. Under optimum conditions, Ablank = 0.020±0.002 and A100 ppb As
= 0.105±0.002 (blank NOT subtracted). Excess Ethyl Violet is hydrolyzed to minimize the blank.
All path lengths are 1 cm. Here is spectral data and the structure of Ethyl Violet:
a) If measurements were made before the excess
Ethyl Violet was hydrolyzed, would the results
of the measurement give an estimate for [As]
that is high, low, or accurate? Explain your
reasoning. (5) (Fig. 1 will help you)
The background drops with time as Ethyl Violet is
hydrolyzed. A decreases with time until it reaches
the steady state value. Thus if the measurement
were made too soon, A would be too high, and thus
the estimated [As] would be too high.
b) From the precision of the measurements,
estimate the detection limit for arsenic. (5)
A is measured ±0.002. The detection limit occurs when the
signal = 3 times the standard deviation of the blank. Thus
ADL = 0.006. 100 ppb gives net absorption of 0.105 – 0.02 =
0.085. 100 ppb/0.085 = DL/0.006. Detection limit = 6/85* 100
ppb = 7 ppb. Note: if you said ADL = 0.002, you will get partial
credit.
c) Assuming complete reaction of As to form the complex, what is the molar absorptivity of the
complex at 612 nm? Atomic weight of As is 75 g/mole. (5)
100 ppb = 100ng/mL = 100μg/L. (100μg/L)/(75 g/mol) = 1.33 μmol L-1. 0.085 (net absorbance) =
1 cm * ε * 1.33 μM. ε = 0.085/1.33×10-6 = 6.4×104 L mol-1 cm-1.
d) The working curve is linear to 300 ppb. As you can see in the caption to Figure 1, [Ethyl Violet]
is 4.5×10-5 M. Based on the available information, why does the working curve become nonlinear
at 300 ppb? Explain your reasoning. (5)
We already know 100 ppb = 1.33 μM. 300 ppb = 3*1.33 μM = 4 μM. The complex requires 3 Ethyl
Violet molecules, so we consume 3*4 = 12 μM EV to detect 300 ppb As. But we start with 45 μM
EV. Thus, we have consumed 12/45 = ¼ of the EV. Even with an infinite equilibrium constant, the
highest signal we can get would come from 45/12 * 300 ppb = 1.125 ppm As. But the equilibrium
constant is not infinite, so we get incomplete reaction when we have used up some of the EV, and the
curve becomes nonlinear.
e) You may purchase a spectrophotometer to do these measurements. Spectrophotometers with
resolution 0.1 nm or 1 nm are available. Would you expect the instrument with 0.1 nm resolution
to give better results than the instrument with 1 nm resolution? Explain. (5)
There is very little structure in the spectrum. Changes occur over intervals ~ 10 nm, so there should
be little difference in response for the two spectrometers.

f) This method is used to assay water from Hoan Kiem Lake. 100 mL of lake water is filtered to
remove algae and sediment. 10 mL of the filtered water sample is mixed with 1 mL of 0.2 M
KIO3, 10 mL of 3.6 M HCl, 10 mL of 0.016 M (NH4)2MoO4, 1 mL of 4.5 mM Ethyl Violet, and
diluted to 100 mL. Absorbance of this mixture after half an hour (the conditions under which the
working curve was obtained) is 0.236. What is the concentration of arsenic in the lake? (5)
In assay, 0.236 = 0.02 + 0.085 CAs, with C in units of 100 ppb. CAs = 0.216/0.085 * 100 ppb = 254
ppb. However, we took 10 mL of lake water and diluted it to get the solution in the
spectrophotometer cell. CLake = 100 mL/10mL * 254 ppb = 2.54 ppm. Note: I hope the data that I
made up for this problem are too high. 2.54 ppm is a HUGE amount of arsenic. On the other hand,
notice how dilution during assay can mean that low detection limits for a method do not always mean
that there is a low detection limit in the original sample.
4. Elemental Analysis. You want to assay the ocean water from Ha Long Bay for Na, K, Ca, and
Mg.
a) Would you choose atomic emission or atomic absorption? Explain your choice. (5)
These are easily excited elements, so atomic EMISSION is preferred.
b) Sea water typically has 10800 ppm Na, 390 ppm K, 410 ppm Ca, and 1290 ppm Mg. Would
you use undiluted sea water in your method, or would you dilute the water 100:1 with
distilled, deionized water? Explain why. (5)
At high concentrations, the alkali metals easily ionize and so change the temperature of the flame and
the extent of ionization of other elements. Diluting 100:1 gets the concentrations down so that there
will not be ionization interference. The working curves are likely to be more linear than at high
concentrations.
c) Would you assay Mg by using a working curve for MgCl2 in distilled water or by doing
standard additions in the diluted ocean water? Explain. (7)
Standard additions are preferred; that way, any matrix effect from Na is compensated. The Mg extent
of ionization will be different in the absence of a 10 times excess of Na.