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CHM 3120 - Spring, 2009 EXAM #3

1.(20) A monochromatic light wave has a frequency of 1.118 X 1015s-1. (a) What is the wavelength (in nm) of this light wave in a vacuum? (b) What is the wavelength in glass that has a refractive index of 1.25? (c) What is the wavenumber (in cm-1)? (d) What general region of the electromagnetic spectrum does this light reside in? a) c 3 x108 m / sec = = = 2.683x10 7 m = 268.3nm 15 1 v 1.118 x10 sec c 3 X 10 8 m / sec = = 2.40 X 10 8 m / sec n 1.25 2.40 X 10 8 m / sec = 2.14 X 10 7 m = 214nm = = 15 1 1.118 X 10 sec n= c ; =

b)

c)

~ x 10 2 m / cm = 3.727 x10 4 cm 1 = 37,270cm 1 = ~= 7 2.683x10 m (46,500cm 1 in glass)

d)

UV

(Or UV - Visible)

CHM 3120 Spring, 2009; Exam 3, Page 2

2.(15) The top figure below is an absorption spectrum of a particular chemical, and includes the bandpass of the instrument used to obtain the spectrum. NOTE that this bandpass is the same at wavelengths A and B. The bottom figure includes calibration curves taken at these two wavelengths. Identify which calibration curve was obtained at wavelength A and which was obtained at B. Just mark the curves as A or B. What is the origin of the curvature in the dashed calibration curve?

The curvature in B is due to the bandpass of the momochromator used in the instrument. Beers Law is strictly valid only for monocharomatic radiation. However, the non-linear response produced by transmitting multiple wavelengths can be minimized if you take measurements at an absorption maximum.
A

CHM 3120 Spring, 2009; Exam 3, Page 3

3.(20) A 3.5 X 10-5 M solution of N-methylcarbazole in a 5 cm cell exhibits a transmittance of 21% when irradiated with UV radiation at 266 nm. (a) What is the molar absorptivity of N-methylcarbazole at 266 nm? (b) What would the transmittance be if the cell path length was doubled to 10 cm?

A = log T = bC

a)

log T log(0.21) = = 3.9x10 3 L / cm M bC (5)(3.5x10 5 )

log T = bC = (3.9 x10 4 )(10)(3.5x10 5 )

b)

log T = 1.365 T = 4.31x10 2 = 4.3%

OR

( log T) 2 b 2 = ( log T)1 b1 log T2 = ( log T1 )(b 2 ) = 1.356 b1

T2 = 4.41%

(NOTE THE ROUND OFF ERROR!!!)

CHM 3120 Spring, 2009; Exam 3, Page 4

4.(20) Nitrite ion, NO2-, is suspected of forming cancer-causing nitrosamines when present in food that is cooked at high temperatures (e.g. filet mignon). A simple and rapid spectrophotometric method has therefore been developed for measuring NO2- in food. The method relies on a series of reactions between nitrite, sulfanilic acid and aminonaphthalene to form an intensely colored product with an absorption maximum at 520 nm. Use the following data to calculate the concentration (in g NO2-/g filet mignon) in this steak sample. After the reactions with sulfanilic acid and aminonaphthalene, a 50 mL extract from a 20 g filet sample gave an absorbance of 0.622 10 L of a 7.50 X 10-4 g/mL standard solution of NO2- was then added to another 50 mL extract and the reactions again were carried out; this solution had an absorbance of 0.967. NOTE that 10 L is such a small volume relative to 50 mL, no volume corrections are necessary in these calculations.

C V Cx = s s VT

7.50 x10 4 10 x10 3 0.622 Cx = (50) 0.967 0.622 C x = 2.70 x10 7 g / mL

A (x ) ; A A (x ) (x +s )

)(

C s = 7.50 x10 4 g / mL
Where:

Vs = 10 x10 3 mL A (x ) = 0.622 A (x +s ) = 0.967

Now, in 50mL of extract there are:

(2.70x10

g / mL (50mL) = 1.352x10 5 g = 13.52g

AND in 20g of filet there are:

13.52 g = 0.676 g/g of filet 20 g

CHM 3120 Spring, 2009; Exam 3, Page 5

5.(15) Below are plotted the relative concentration errors (RSD) (or C/C) for a Spectronic 20 UV-Vis spectrometer. This spectrometer exhibits a constant error in transmittance measurement (T), regardless of the intensity of light striking the detector. Use the error at Absorbance = 1.0 (about 2.6%) to calculate this T.

NOTE that the relative concentration error RSD is given by the following equation:

C T = C T ln T
Thus, if C/C = 2.6% (0.026) at Abs = 1.0 (T = 0.1), then

C 3 T = T * ln(T ) = (0.026 )(0.1)(2.30) = 5.99 X 10 = 0.599% C

CHM 3120 Spring, 2009; Exam 3, Page 6

6.(10) The figure below represents a spectrophotometric titration. What is the absorbing species in this titration?

ABS

Vol of titrant

Analyte