21.1 Why is a Cu(NH solution blue?

3)2 4
The solution has a blue tone due to the presence of Cu, the molecule absorbs or reflects the
different colors except blue, as well as absorbing the yellow color will emit a
blue coloring.
21.2 What relationship exists between
a) absorbance and transmittance?
They are inversely proportional, and each of them can be defined in terms of the
another.
b) absorptivity a and molar absorptivity ε
they express the same term in Beer’s Law, but with different units, the second with
mole units, as they are related to the molecular weight of the substance.

21.4 describe the difference between the 'true' deviations of Beer’s law and those due to
instrument or chemical factors
The true deviations come from changes in the refractive index of the system.
Analytical and instrumental is due to non-chromatized light and the chemical factors have to
see with the reactions and the kinetics of color.

21.5 How do an electronic transition and a transition by absorption compare and how do they differ?
vibration?
In the electronic transition, energy is absorbed by exciting the e-- transforming to a level of
more energy and when they return they emit photons in the form of light, while the vibrational
produces a vibration in the molecule that can be absorbed by its interaction with the medium. It
they resemble each other in that both have an absorption and emission of energy.

21.6 calculate the frequency in Hertz of

a) a beam of X-rays with a wavelength of 2.65 Å
v=3x10^8/2.65Å (1x10-10^m/1Å) =1.13x10^18 Hz
b) a copper emission line at 211nm
v = 3 x 10^8 / 211 nm (1 x 10^-9 m / 1 nm) = 1.42 x 10^15 Hz

c) the line at 694.3 nm produced by a ruby laser

v=3x10^8/694.3nm (1x10-9^m/1nm) =4.32x10^14 Hz
d) the output of a CO2 laser at 10.6μm
v=3x10^8/10.6μm (1x10-6^m/1μm) =4.32x10^13 Hz

21.8 A simple infrared spectrophotometer covers a wavelength range of 3 to 5 um.

Express the interval in:
wave number
a) The wave number is the reciprocal of the wavelength; also, its units are cm.-1For that
so much

(3x10-6m)(100cm) equals three times ten-4cm

1m
(15x10-6m)((100cm)=1.5x10-3cm
1m
1
~v=1= 3333.3333 cm-1
3x10^−4cm
1
~v2=1= 666.6667 cm-1
3 x 10^-3 cm

The wavelength range is from 3.333,333 to 666,66667 cm-1

b) c = v * λ v=c/λ

x 108 m/s
v1= c/λ =3 1x10^14 Hz
2x10^-6m

8
v2=c/λ =3x10 m/s
= 1x10^11 Hz
1.5 x 10^-3 m
the frequency range is from 1x10^14 Hz to 2x10^11 Hz

21.12 Calculate the wavelength of

a) the sodium line of 589 nm in an aqueous solution that has a refractive index of 1.35
b) A signal output from a ruby laser at 694.3 nm when passing through a piece of quartz that
it has a refractive index of 1.55

λ(1)
a) n = c/v =
λ (2)
λ(2)=λ(1)/n =589 nm= 436.29 nm
1.35

b)λ(2)= λ(1)/n =694.3 nm447.93 nm

1.55

21.13. What are the units of absorptivity when the path of the ray is given in
centimeters and the concentration is expressed in micrograms per liter?
parts per million
amolar=
( )( )
micrograms per liter
a=
( )( )
c) weight/volume percentage
A=
grams per liter

21.14. Express the following absorbances as percentage transmittance:

0.0510
%T=10-A100%
88.92%
b) 0.918
12.0781%
0.379
T=41.78%
d) 0.261
54.827%
0.485
T=32.73%
f) 0.702
19.86%

21.15. Convert the following transmittance data into absorbance:

25.5%
A= -log ( )
100
A= 0.5934

b) 0.567
A = -log(0.567)
A= 0.246

c) 32.8%
A= -log( )
100
A=0.4841

d) 3.58%
A= -log ( )
100
A=1.4461

0.085
A=1.0705

f) 53.8%
A = -log( )
100
A=0.2692

21.17 Calculate the absorbances of solutions that have a transmittance of half of those that
they have the solutions to problem 21.15

T 25.5% 0.567 32.8% 3.58% 0.085 53.8%

A 0.5439 0.2464 0.4841 1.4461 1.07050 0.2692

A = -log T
 T 12.75% 0.2835 16.4% 1.79% 0.0425 26.9%
A 0.8944 0.5474 0.7851 1.7471 1.3716 0.5702

21.18. Complete the missing amounts in the table shown. When necessary, use
a value of 200 for the analyte mass

A %T
-1 -1 -1 -1
0.172 67.29 4.23 times 103 21.15 1.00 4.066x10-5 8.13
b) 0.347 44.9 3.42x104 0.0258 0.75 1.35x10-4 17.93
0.520 30.19 7.95 times 103 39.75 1.00 6.54 times 10 13
-5

d) 0.402 39.6 2.04x10-4 0.0912 2.504 7.21x10-5 1.76

0.637 23.02 3.73x103 18.65 0.100 1.71 times 10 0.341
-3

f) 0.077 83.6 1.038x10-4 0.0452 1.00 8.07 times 10-6 11.41

0.798 15.92 5.7 times 103 0.0158 1.50 5.03 times 10-3 33.6
h) 0.954 11.1 1.35 times 104 67.5 0.9995 7.07 times ten-5 0.0141
1.281 5.23 9.78x103 48.9 4.9x10-3 2.673 times 10-35.24
0.179 66.22 4.016x10-4 12.44 1.00 7.19 times 10-5 14.38

21.19. A solution that contains 4.48 ppm of KMnO4it has a transmittance of 0.309 in a
cell of 1.00 cm at 520nm. Calculate the molar absorptivity of KMnO.4.
A = -log (T) = 0.510
0.510
E= 0.1135L/cm*mg
∗ 1 times 4.48

21.21 At 580 nm, the wavelength of its maximum absorption, the Fe(SNC) complex2+has
a molar absorptivity of 7x103L mol-1cm-1Calculate
a) the absorbance of a 2.5 x 10 solution-5M of the complex at 580 nm in a 1 cm cell
A=abc
A=(7x103L mol-1cm-1) ( 2.5 x 10-5mol L-1(1 cm) = 0.175
b) the absorbance of a solution in which the complex has a concentration double that of a)
abc
A=(7x103L mol-1cm-12.5 x 10-5mol L-1(1 cm) = 0.350
c) the transmittance of the solutions described in a) and b)
10%-A100%
For a) %T=10^(-0.175) *100= 66.83%
For b) %T=10^(-0.350) *100= 44.66%
d) the absorption of a solution that has a transmittance of half of that described in a)
T = 66.83% / 2 = 33.415%
A=-log(%T/100%)
A=-log(0.33415)= 0.476

21.22 A aliquot of 2.5 mL of a solution contains 3.8 ppm of iron(III) and is treated with an excess
from KSCN and it is diluted to 50 mL. What is the absorbance of the resulting solution at 58 nm in a
2.5 cm cell?
C1V1=C2V2
C2=0.19 ppm
a = ε/PM
a = 0.06144 L/mg^-1 cm^-1
A=abc
A=(0.06144)(2.5)(0.19)= 0.02918

21.23 A solution that contains a complex formed between Bi(III) and thiourea has a
molar absorptivity of 9.32x10^3 L/mol*cm at 470nm.

a) What is the absorbance of a 6.24x10^-5M solution of the complex at 470nm in a cell?

of 1.00cm?

Absorbance formula

= ∗ ∗

= 9.32x10^3L/mol * cm *(6.24x10-5M) ∗ 1 = 0.581568

b) What is the transmittance percentage of the solution described in a)?

transmittance

% = 10− ∗ 100

In this way

% = 10-0.581568∗ 100= 26.2078%

c) What is the molar concentration of the complex in a solution that has the same
absorbance that in a) when measured at 470 nm in a 5.00cm cell?

concentration
 =
∗
0.581568
= = 1.248 10^ - 6
9.32x10^3L/mol ∗ cm ∗5

The complex formed between Cu(I) and 1,10-phenanthroline has a molar absorptivity of 7000.
L mol^-1*cm^-1 at 435nm, the wavelength for maximum absorption. Calculate.

a) The absorbance of a 8.50*10^-1M solution of the complex when measured in a cell of

1.00cm to 435nm.

Absorptivity formula

= ∗ ∗

= 7000 ∗ (8.50∗ 10-1) ∗ 1 = 0.5950

∗

b) The percentage of transmittance of the solution in a).

transmittance

% = 10− ∗ 100

In this way

% = 10-0.5950∗ 100= 25.4097%

c) The concentration of a solution that in a 5.00 cm cell has the same absorbance as the
solution in a).

concentration

=
∗
0.5950
= = 1710^ -6
7000 ∗5
∗
c) The length of the path of the radiation through a 3.40x10^-3M solution of the complex
What is needed for the absorbance to be equal to that of the solution in a)

length

=
∗
0.5950
= = 35
7000 ∗ 3.40x10^ - 3M
∗

21.25. A solution that has a 'real' absorbance [A = LOG (IOFrom 2.10 it was placed in a
spectrophotometer that had a periodic radiation level (IO/I) of 0.75%. What absorbance A´
Would it be measured? What would the % of error be?

A= -log ( )
100
A=2.12

Ea2.12 - 2.10 Er= Eatrue value

Ea0.02 Er=0.95

21.26 A compound X is analyzed by UV/Vis spectrophotometry. A standard curve is prepared.

calibration with standard solutions of this compound yields the following results:

A ppm
0.36 1.5
0.44 2.5
0.59 3.5
0.7 4.5
0.24 1

Find the slope and the intersection of the calibration curve, the standard error in Y, the
concentration of the solution with unknown concentration and its standard deviation.

Build a calibration curve graph and determine the concentration of a sample on it.
of unknown concentration.
 Problem 21.26 y = 4.8636x - 0.1166
R² = 0.9999
4.5
4
4
3.5
3
3
2.5
2
2
1.5
11
1
0.5
0
0.22 0.32 0.42 0.52 0.62 0.72 0.82 0.92

21.27 The common method for determining phosphorus in urine consists of treating the sample with
molybdenum (VI) after removing the proteins and subsequent reduction of the 12-molybdophosphate complex
with ascorbic acid. The reduced species gives the solution an intense blue color called
molybdenum blue, whose absorbance can be measured at 650 nm. A 24-hour urine sample from a
The patient gave a volume of 1122mL. A 1.00mL aliquot of the sample was treated with Mo(VI) and
ascorbic acid and was diluted to a volume of 50.00 mL. A calibration curve was prepared with
aliquots of 1.00mL of standard phosphate solutions treated the same as the urine sample. The
absorbances of the standard solutions and the urine sample. The absorbances of the solutions
standard and of the sample, measurements at 650nm were as follows

0.23 1
0.436 2
0.638 3
0.848 4
0.518 2.4027
 Problem 21.26 y = 4.8636x - 0.1166
R² = 0.9999
4.5
4
4
3.5
3
3
2.5
2
2
1.5
1
1
0.5
0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9