CHAPTER 0

THE ANALYTICAL PROCESS

0-1.

Qualitative analysis finds out what is in a sample. Quantitative analysis measures

how much is in a sample.

0-2.

Steps in a chemical analysis:

(1) Formulate the question: Convert a general question into a specific one that
can be answered by a chemical measurement.
(2) Select the appropriate analytical procedure.
(3) Obtain a representative sample.
(4) Sample preparation: Convert the representative sample into a sample suitable
for analysis. If necessary, concentrate the analyte and remove or mask
interfering species.
(5) Analysis: Measure the unknown concentration in replicate analyses.
(6) Produce a clear report of results, including estimates of uncertainty.
(7) Draw conclusions: Based on the analytical results, decide what actions to
take.

0-3.

Masking converts an interfering species to a noninterfering species.

0-4.

A calibration curve shows the response of an analytical method as a function of

the known concentration of analyte in standard solutions. Once the calibration
curve is known, then the concentration of an unknown can be deduced from a
measured response.

0-5.

(a) A homogeneous material has the same composition everywhere. In a

heterogeneous material, the composition is not the same everywhere.
(b) In a segregated heterogeneous material, the composition varies on a large
scale. There could be large patches with one composition and large patches
with another composition. The differences are segregated into different
regions. In a random heterogeneous material, the differences occur on a fine
scale. If we collect a reasonable-size portion, we will capture each of the
different compositions that are present.
(c) To sample a segregated heterogeneous material, we take representative
amounts from each of the obviously different regions. In panel b in Box 0-1,
66% of the area has composition A, 14% is B, and 20% is C. To construct a

Chapter 0

representative bulk sample, we could take 66 randomly selected samples

from region A, 14 from region B, and 20 from region C. To sample a
random heterogeneous material, we divide the material into imaginary
segments and collect random segments with the help of a table of random
numbers.
0-6.

We are apparently observing interference by Mn2+ in the I- analysis by method

A. The result of the I- analysis is affected by the presence of Mn2+. The greater
the concentration of Mn2+ in the mineral water, the greater is the apparent
concentration of I- found by method A. Method B is not subject to the same
interference, so the concentration of I- is low and independent of addition of
Mn2+. There must be some Mn2+ in the original mineral water, which causes
method A to give a higher result than method B even when no Mn2+ is
deliberately added.

CHAPTER 1
MEASUREMENTS

A note from Dan: Dont worry if your numerical answers are slightly different
from those in the Solutions Manual. You or I may have rounded intermediate
results. In general, retain many extra digits for intermediate answers and save
your roundoff until the end. We'll study this process in Chapter 3.
1-1.

(a) meter (m), kilogram (kg), second (s), ampere (A), kelvin (K), mole (mol)
(b) hertz (Hz), newton (N), pascal (Pa), joule (J), watt (W)

1-2.

Abbreviations above kilo are capitalized: M (mega, 106), G (giga, 109), T (tera,
1012), P (peta, 1015), E (exa, 1018), Z (zetta, 1021) and Y (yotta, 1024).

1-3.

(a) mW
(b) pm

=
=

milliwatt
picometer

=
=

10-3 watt
10-12 meter

(c)
(d)
(e)
(f)
(g)
(h)

=
=
=
=
=
=

kiloohm
microfarad
terajoule
nanosecond
femtogram
decipascal

=
=
=
=
=
=

103 ohm
10-6 farad
1012 joule
10-9 second
10-15 gram
10-1 pascal

1-4.

1-5.

k
F
TJ
ns
fg
dPa

(a) 100 fJ or 0.1 pJ

(d) 0.1 nm or 100 pm

(b) 43.172 8 nF

(e) 21 TW

(c) 299.79 THz or 0.299 79 PHz

(f) 0.483 amol or 483 zmol

(a) 5.4 Pg = 5.4 1015 g.

5.4 1015 g

1 kg
= 5.4 1012 kg of C
1 000 g

(b) The formula mass of CO2 is 12.010 7 + 2(15.999 4) = 44.009 5

44.009 5 kg CO2
5.4 1012 kg C 12.010 7 kg C = 2.0 1013 kg CO2
(c) 2.0 1013 kg CO2

1 ton
= 2.0 1010 tons of CO2
1 000 kg

2.0 1010 tons

= 4 tons per person
5 10 9 people

Chapter 1

1-6.

Table 1-4 tells us that 1 horsepower = 745.700 W = 745.700 J/s.

745.700 J / s
100.0 horsepower = (100.0 horsepower )
= 7.457 104 J/s.
horsepower

7.457 104
4.184

1-7.

J
cal

J
s

3 600

= 6.416 107

cal
.
h

J 1 day 1 h
6 cal
2.2 10
4.184

cal 24 h 3600 s
day

(a)
= 2.0 J/(s.kg)

kg
(120 pound ) 0.453 6

pound

= 2.0 W/kg
Similarly, 3.4 103

kcal
3.0 J/(s.kg) = 3.0 W/kg.
day

(b) The office workers power output is

J 1 day
6 cal
2.2 10
4.184

cal
day
24 h

h
J
= 1.1 102 = 1.1 102 W

3600 s
s

The persons power output is greater than that of the 100 W light bulb.
1-8.

J
J 1 h
3 Btu
= 1.47 103 W
5.00 10
1055.06
= 1.47 103

s
3600
s
Btu
h

1-9.

mile
m 1 inch 1 foot 1 mile

(a) 1 000

= 0.621 37 km

km 0.025 4 m 12 inch 5 280 foot

100 km 0.621 37 miles 3.785 4 L

miles
(b)

= 51 gallon

km
gallon
4.6 L

(c) The diesel engine produces 223 g CO2/km, which we will convert into g/mile:

g CO2
g CO 2
1 km

= 359 mile
223

km 0.621 37 mile

In 15 000 miles, CO2 = (15 000 miles)(359 g/mile) = 5.38 106 g or 5.38
103 kg = 5.38 metric tons. The gasoline engine produces 266 g CO2/km,

Measurements

which we convert into 428 g/mile or 6.42 metric tons in 15 000 miles.
1-10.

m
Newton = force = mass acceleration = kg
s2
m2
m .
Joule = energy = force distance = kg m = kg

s2
s2

m
kg
Pascal = pressure = force / area = kg /m2 =
m s2
s2

1-11.

mg
0.03
2

m day

1g
1000 m (535 km 2 )
1000 mg

km

1 kg

1000 g

1-12.

1 ton

1000 kg

day
ton
365
= 6

year
year

(a) molarity = moles of solute / liter of solution

(b) molality = moles of solute / kilogram of solvent
(c) density = grams of substance / milliliter of substance
(d) weight percent = 100 (mass of substance/mass of solution or mixture)
(e) volume percent = 100 (volume of substance/volume of solution or mixture)
(f) parts per million = 106 (grams of substance/grams of sample)
(g) parts per billion = 109 (grams of substance/grams of sample)
(h) formal concentration = moles of formula/liter of solution

1-13.

Acetic acid (CH3CO2H) is a weak electrolyte that is partially dissociated. When

we dissolve 0.01 mol in a liter, the concentrations of CH3CO2H plus CH3CO2add to 0.01 M. The concentration of CH3CO2H alone is less than 0.01 M.

1-14.

1-15.

32.0 g / [(22.990 + 35.453) g/mol] = 0.548 mol NaCl

0.548 mol / 0.500 L = 1.10 M

mol CH3OH
1.71
(0.100 L solution ) = 0.171 mol CH3OH

L
solution

Chapter 1

32.04 g
(0.171 mol CH3OH )
mol CH3OH

1-16.

(a) 19 mPa = 19 10-3 Pa.

= 5.48 g

19 10-3 Pa

1bar
5

10 Pa

= 1.9 10-7 bar

(b) T (K) = 273.15 + C = 273.15 70 = 203 K

n
P
=
V
RT =

1-17.

1 ppm =

1.9 107 bar

= 1.1 10-8 M = 11 nM
L bar
203 K
0.08314
mol K

1 g solute
. Since 1 L of dilute solution 103 g,
106 g solution

1 ppm = 10-3 g solute/L ( = 10-3 g solute / 103 g solution).

Since 10-3 g = 103 g, 1 ppm = 103 g/L or 1 g/mL.
Since 10-3 g = 1 mg, 1 ppm = 1 mg/L.
1-18.

0.2 ppb means 0.2 10-9 g of C20H42 per g of rainwater

g C20H42
0.2 10-6 g C20H42
= 0.2 10-6 1 000 g rainwater
.
L rainwater
0.2 106 g / L
282.55 g / mol

1-19.

1-20.

= 7 10-10 M

g HClO 4
0.705
(37.6 g solution ) = 26.5 g HClO4

g
solution

37.6 g solution 26.5 g HClO4 = 11.1 g H2O

g solution
mL
(a) 1.67
= 1.67 103 g solution
1000
L
mL

g HClO4
3
(b) 0.705
(1.67 10 g solution ) = 1.18 103 g HClO4

g solution

(c) (1.18 103 g ) / (100.46 g /mol) = 11.7 mol

1-21.

mol KI
molality = kg solvent
200 g KI
200 g KI
20.0 wt% KI = 1 000 g solution = 800 g H O
2
To find the grams of KI in 1 kg of H2O, we set up a proportion:

Measurements

200 g KI
x g KI
=
800 g H2O
1 000 g H2O x = 250 g KI
But 250 g KI = 1.51 mol KI, so the molality is 1.51 m.
1-22.

(a)

150 1015 mol/cell

amol
= 6.0 vessicle
4
2.5 10 vesicles/cell

molecules
6
(b) (6.0 1018 mol ) 6.022 1023
= 3.6 10 molecules
mol

4
(200 10-9 m)3 = 3.35 10-20 m3;
(c) Volume =
3
3.35 1020 m
10

(d)

1-23.

= 3.35 10-17 L

m /L

10 1018 mol
3.35 1017 L

80 10-3 g
180.2 g / mol

= 0.30 M

= 4.4 10-4 mol;

4.4 10-4 mol

-3

100 10 L

= 4.4 10-3 M;

Similarly, 120 mg/100 L = 6.7 10-3 M.

1-24.

(a) Mass of 1.000 L = 1.046

mL
g
1 000
1.000 L = 1 046 g
mL
L

Grams of C2H6O2 per liter = 6.067

g
mol
g
= 376.6 L
62.07
L
mol

(b) 1.000 L contains 376.6 g of C2H6O2 and 1 046 376.6 = 669 g of H2O
= 0.669 kg
Molality =
1-25.

6.067 mol C2H6O2

mol C2H6O2
=
9.07
= 9.07 m
0.669 kg H2O
kg H2O

Shredded wheat: 1.000 g contains 0.099 g protein + 0.799 g carbohydrate

Cal
Cal
0.099 g 4.0
+ 0.799 g 4.0
= 3.6 Cal
g
g
Doughnut: 1.000 g contains 0.046 g protein + 0.514 g carbohydrate + 0.186 g fat
Cal
Cal
Cal
0.046 g 4.0
+ 0.514 g 4.0
+ 0.186 g 9.0
= 3.9 Cal
g
g
g
Cal
Cal
In a similar manner, we find 2.8 g for hamburger and 0.48 g for apple.
There are 16 ounces in 1 pound, which Table 1-4 says is equal to 453.592 37 g

Chapter 1

g
28.35 ounce.

1-26.

To convert Cal/g to Cal/ounce, multiply by 28.35:

Shredded Wheat
Doughnut
Hamburger

Apple

Cal/g
Cal/ounce

0.48
14

3.6
102

3.9
111

2.8
79

1 000 kg
Mass of water = (225 m)2 (10.0 m )
= 1.59 109 kg
3
m

-3
1.6 10 g F
1.6 ppm =
kg H2O

Mass of F required =

g F
1.6 103

kg H 2O

(1.59 109 kg H 2O ) = 2.5 106 g F.

(If we retain three digits for the next calculation, this last number is 2.54
106.)
The atomic mass of F is 18.998 and the formula mass of H2SiF6 is 144.09. One
mole of H2SiF6 contains 6 moles of F.
mass of F
6 18.998
2.54 106 g F
6
=
=
mass of H2SiF6
x g H2SiF6 x = 3.2 10 g H2SiF6
144.09
1-27.

(a) PV = nRT

L bar
(1.000 bar)(5.24 10-6 L) = n 0.08314
(298.15K )
mol K

n = 2.11 10-7 mol 2.11 10-7 M

(b) Ar: 0.934% means 0.009 34 L of Ar per L of air

L . bar
(1.000 bar)(0.009 34 L) = n 0.083 14
(298.15 K)
mol . K

n = 3.77 10-4 mol 3.77 10-4 M

Kr: 1.14 ppm 1.14 L Kr per L of air 4.60 10-8 M
Xe: 87 ppb 87 nL Xe per L of air 3.5 10-9 M
mol
g
61.83
= 6.18 g in a 2 L volumetric flask
L
mol

1-28.

2.00 L 0.050 0

1-29.

Weigh out 2 0.050 0 mol = 0.100 mol = 6.18 g B(OH)3 and dissolve in 2.00
kg H2O.

Measurements

1-30.

1-31.

Mcon . Vcon = Mdil . Vdil

mol
0.80
(1.00 L ) =
L

We need 1.00 L 0.10

4.0 g NaOH
0.50

1-32.

g NaOH

mol

0.25
Vdil Vdil = 3.2 L
L

mol
= 0.10 mol NaOH = 4.0 g NaOH
L

= 8.0 g solution

g solution

Mdil
1.00 M
(a) Vcon = Vdil M
= 1 000 mL 18.0 M = 55.6 mL

con
(b) One liter of 98.0% H2SO4 contains (18.0 mol )(98.079 g/ mol ) = 1.77 103
g of H2SO4. Since the solution contains 98.0 wt% H2SO4, and the mass of
H2SO4 per mL is 1.77 g, the mass of solution per milliliter (the density) is
1.77 g H 2SO 4 / mL
0.980 g H 2SO 4 / g solution

= 1.80 g solution/mL

1-33.

2.00 L of 0.169 M NaOH = 0.338 mol NaOH = 13.5 g NaOH

g solution
density = mL solution
13.5 g NaOH
g
=
= 1.52 mL

g NaOH
(16.7 mL solution) 0.534

g
solution

1-34.

FM of Ba(NO3)2 = 261.34
4.35 g of solid with 23.2 wt% Ba(NO3)2 contains
(0.232)(4.35 g) = 1.01 g Ba(NO3)2
mol Ba2+ =

(1.01 g Ba(NO3 ) 2 )
(261.34 g Ba(NO3 )2 / mol)

= 3.86 10-3 mol

mol H2SO4 = mol Ba2+ = 3.86 10-3 mol

(3.86 10-3 mol)
volume of H2SO4 =
(3.00 mol/L) = 1.29 mL
1-35.

25.0 mL of 0.023 6 M Th4+ contains

(0.025 0 L)(0.023 6 M) = 5.90 10-4 mol Th4+
mol HF required for stoichiometric reaction = 4 mol Th4+ = 2.36 10-3 mol
50% excess = 1.50(2.36 10-3 mol) = 3.54 10-3 mol HF

10

Chapter 1

Required mass of pure HF = (3.54 10-3 mol)(20.01 g/mol) = 0.070 8 g

(0.070 8 g HF )
= 14.4 g
Mass of 0.491 wt% HF solution =
(0.004 91 g HF / g solution)
1-36.

Concentrations of reagents used in an analysis are determined either by weighing

out supposedly pure primary standards or by reaction with such standards. If the
standards are not pure, none of the concentrations will be correct.

1-37.

The equivalence point occurs when the exact stoichiometric quantities of reagents
have been mixed. The end point, which comes near the equivalence point, is
marked by a sudden change in a physical property brought about by the
disappearance of a reactant or appearance of a product.

1-38.

In a blank titration, the quantity of titrant required to reach the end point in the
absence of analyte is measured. By subtracting this quantity from the amount of
titrant needed in the presence of analyte, we reduce the systematic error.

1-39.

In a direct titration, titrant reacts directly with analyte. In a back titration, a

known excess of reagent that reacts with analyte is used. The excess is then
measured with a second titrant.

1-40.

Primary standards are purer than reagent-grade chemicals. The assay of a

primary standard must be very close to the nominal value (such as 99.95
100.05%), whereas the assay on a reagent chemical might be only 99%. Primary
standards must have very long shelf lives.

1-41.

Since a relatively large amount of acid might be required to dissolve a small

amount of sample, we cannot tolerate even modest amounts of impurities in the
acid for trace analysis. Otherwise, the quantity of impurity could be greater than
quantity of analyte in the sample.

1-42.

40.0 mL of 0.040 0 M Hg2(NO3)2 = 1.60 mmol of Hg2+

2 , which will require 3.20
3.20 mmol
mmol of KI. This is contained in volume = 0.100 mmol/mL = 32.0 mL.

1-43.

108.0 mL of 0.165 0 M oxalic acid = 17.82 mmol, which requires

2 mol MnO4-

(17.82 mol H2C2O4) = 7.128 mmol of MnO - .

4
5
mol
H
C
O
2 2 4

11

Measurements

7.128 mmol / (0.165 0 mmol/mL) = 43.20 mL of KMnO4.

Another way to see this is to note that the reagents are both 0.165 0 M. Therefore,
2

volume of MnO4- = 5(volume of oxalic acid) .

5

For second question, volume of oxalic acid = 2(volume of MnO4-) = 270.0 mL.
1-44.

1-45.

1-46.

1.69 mg of NH3 = 0.099 2 mmol of NH3. This will react with 2 (0.099 2) =
0.149 mmol of OBr-. The molarity of OBr- is 0.149 mmol/1.00 mL = 0.149 M.
0.333 7 g
mol sulfamic acid = 97.094 g/mol = 3.4369 mmol
3.4369 mmol
molarity of NaOH = 34.26 mL = 0.100 3 M
HCl added to powder = (10.00 mL)(1.396 M) = 13.96 mmol
NaOH required = (39.96 mL)(0.100 4 M) = 4.012 mmol
HCl consumed by carbonate = 13.96 4.012 = 9.948 mmol
1

mol CaCO3 = 2 mol HCl consumed = 4.974 mmol = 0.4978 g CaCO3

0.4978 g CaCO3
wt% CaCO3 = 0.541 3 g limestone 100 = 92.0 wt%

CHAPTER 2
TOOLS OF THE TRADE

2-1.

The primary rule is to familiarize yourself with the hazards of what you are about
to do and not to do something you consider to be dangerous.

2-3.

Dichromate (Cr2O27 ) is soluble in water and contains carcinogenic Cr(VI).

Reducing Cr(VI) to Cr(III) decreases the toxicity of the metal. Converting
aqueous Cr(III) to solid Cr(OH)3 decreases the solubility of the metal and
therefore decreases its ability to be spread by water. Evaporation produces the
minimum volume of waste.

2-4.

The upper 0 means that the reagent has no fire hazard. The right hand 0
indicates that the reagent is stable. The 3 tells us that the reagent is corrosive
or toxic and we should avoid skin contact or inhalation.

2-5.

The lab notebook must: (1) state what was done; (2) state what was observed; and
(3) be understandable to a stranger.

2-6.

See Section 2.3.

2-7.

The buoyancy correction is 1 when the substance being weighed has the same
density as the weights used to calibrate the balance.

2-8.

0.001 2 g/mL
(14.82 g) 1 8.0 g/mL

m =
= 14.85 g
0.001
2
g/mL

0.626 g/mL

2-9.

The smallest correction will be for PbO2, whose density is closest to 8.0 g/mL.
The largest correction will be for the least dense substance, lithium.

2-10.

0.001 2 g/mL
4.236 6 g 1 8.0 g/mL

m =
= 4.239 1 g
1 0.001 2 g/mL

1.636 g/mL

Without correcting for buoyancy, we would think the mass of primary standard is
less than the actual mass and we would think the molarity of base reacting with
the standard is also less than the actual molarity. The percentage error would be
true mass measured mass
4.239 1 4.236 6
100 =
100 = 0.06%.
true mass
4.239 1

12

13

Tools of the Trade

2-11.

(a) One mol of He (= 4.003 g) occupies a volume of

L bar
(1 mol ) 0.08314
mol K
nRT

V= P =
1 bar

(293.15 K )

= 24.37 L

Density = 4.003 g / 24.37 L = 0.164 g/L = 0.000 164 g/mL

0.000 164 g/mL
(0.823 g) 1

8.0 g/mL

(b) m =
0.000 164 g/mL
1

0.97 g/mL

2-12.

= 0.823 g

(a) (0.42) (2 330 Pa) = 979 Pa

(b) Air density =
(0.003 485)(94 000) (0.001 318)(979)
= 1.11 g/L = 0.001 1 g/mL
293.15

0.0011 g/mL
1
8.0 g/mL
(c) mass = 1.000 0 g

0.0011 g/mL
1

1.00 g/mL

= 1.001 0 g

r2a

2-13.

(6 370 000 m)2

mb = ma 2 = (100.0000 g)
= 99.999 1 g
(6 370 030 m)2
rb

2-14.

TD means to deliver and TC means to contain.

2-15.

Dissolve (0.250 0 L)(0.150 0 mol/L) = 0.037 50 mol of K2SO4 (= 6.535 g, FM

174.26 g/mol) in less than 250 mL of water in a 250-mL volumetric flask. Add
more water and mix. Dilute to the 250.0 mL mark and invert the flask many
times for complete mixing.

2-16.

The plastic flask is needed for trace analysis of analytes at ppb levels that might
be lost by adsorption on the glass surface.

2-17.

(a) With a suction device, suck liquid up past the 5.00 mL mark. Discard one or
two pipet volumes of liquid to rinse the pipet. Take up a third volume past
the calibration mark and quickly replace the bulb with your index finger.
(Alternatively, use an automatic suction device that remains attached to the

14

Chapter 2

pipet.) Wipe excess liquid off the outside of the pipet with a clean tissue.
Touch the tip of the pipet to the side of a beaker and drain liquid until the
bottom of the meniscus reaches the center of the mark. Transfer the pipet to a
receiving vessel and drain it by gravity while holding the tip against the wall.
After draining stops, hold the pipet to the wall for a few more seconds to
complete draining. Do not blow out the last drop. The pipet should be nearly
vertical at the end of delivery.
(b) Transfer pipet.
2-18.

(a) Adjust the knob for 50.0 L. Place a fresh tip tightly on the barrel. Depress
the plunger to the first stop, corresponding to 50.0 L. Hold the pipet
vertically, dip it 35 mm into reagent solution, and slowly release the plunger
to suck up liquid. Leave the tip in the liquid for a few more seconds.
Withdraw the pipet vertically. Take up and discard three squirts of reagent to
clean and wet the tip and fill it with vapor. To dispense liquid, touch the tip
to the wall of the receiver and gently depress the plunger to the first stop.
After a few seconds, depress the plunger further to squirt out the last liquid.
(b) The procedure in (a) is called forward mode. For a foaming liquid, use
reverse mode. Depress the plunger beyond the 50.0 L stop and take in
more than 50.0 L. To deliver 50.0 L, depress the plunger to the first stop
and not beyond.

2-19.

The trap prevents liquid filtrate from being sucked into the vacuum system. The
watchglass keeps dust out of the sample.

2-20.

Phosphorus pentoxide

2-21.

20.214 4 g 10.263 4 g = 9.951 0 g. Column 3 of Table 2-7 tells us that the true
volume is (9.951 0 g)(1.002 9 mL/g) = 9.979 9 mL.

2-22.

0.999 102 6
Expansion = 0.997 047 9 = 1.002 060 8 0.2%. Densities were taken from Table
2-7. The 0.500 0 M solution at 25 would be (0.500 0 M)/(1.002) = 0.499 0 M.

2-23.

Using column 2 of Table 2-7, mass in vacuum =

(50.037 mL )(0.998 207 1 g/ mL ) = 49.947 g.
Using column 3, mass in air =

50.037 mL
= 49.892 g.
1.0029 mL /g

15

Tools of the Trade

2-24.

When the solution is cooled to 20C, the concentration will be higher than the
density at 20C

concentration at 24C by a factor of density at 24C. Therefore, the concentration

needed at 24 will be lower than the concentration at 20C.
0.997 299 5 g/mL
= 0.999 1 M
Desired concentration at 24C = (1.000 M)
0.998 207 1 g/mL

(using the quotient of densities from Table 2-7). The true mass of KNO3

mol
g
needed is 0.500 0 L 0.9991
101.103
= 50.506 g.
mol
L

0.001 2 g/mL
(50.506 g) 1 2.109 g/mL

m' =
= 50.484 g
1 0.001 2 g/mL

8.0 g/mL

2-25.

(a) Fraction within specifications = e-t(ln 2)/tm. If tm = 2 yr and t = 2 yr, then

fraction within specifications = e-2(ln 2)/2 = e-ln 2 = .
(b) Fraction within specifications = 0.95 = e-t(ln 2)/2 yr
ln(0.95) = t(ln 2)/2 t = 2 ln(0.95)/ln 2 = 0.148 yr = 54 days 8 weeks
To solve for t, take the natural logarithm of both sides:

2-26.

Al extracted from glass = (0.200 L)(5.2 10-6 M) = 1.04 10-6 mol

mass of Al = (1.04 10-6 mol)(26.98 g/mol) = 28.1 g
This much Al was extracted from 0.50 g of glass, so
28.1 10-6 g
= 0.005 62 wt%
0.50 g
0.005 62 wt%
Fraction of Al extracted = 0.80 wt% = 0.007 0 (or 0.70% of the Al)

wt% Al extracted = 100

16

Graph of van Deemter Equation

van Deemter Equation
Flow rate Plate height
Constants (mL/min)
(mm)
A=
4
8.194
1.65
6
6.092
B=
8
5.064
25.8
10
4.466
C=
20
3.412
0.0236
30
3.218
40
3.239
50
3.346
60
3.496
70
3.671
80
3.861
90
4.061
100
4.268
Formula:
C5 = $A$6+$A$8/B5+$A$10*B5

9
8

Plate height (mm)

2-27.

Chapter 2

7
6
5
4
3
2
1
0
0

20

40

60

80

Flow rate (mL/min)

100

CHAPTER 3
EXPERIMENTAL ERROR

3-1.

(a) 5

(b) 4

(c) 3

3-2.

(a) 1.237

(b) 1.238

(c) 0.135

3-3.

(a) 0.217

(b) 0.216

(c) 0.217

3-4.

(b) 1.18 (3 significant figures) (c) 0.71 (2 significant figures)

3-5.

(a) 3.71
(b) 10.7
(c) 4.0 101 (d) 2.85 10-6
(e) 12.625 1 (f) 6.0 10-4 (g) 242

3-6.

(a) BaF2 = 137.327 + 2(18.998 403 2) = 175.324 because the atomic mass of Ba

(d) 2.1

(e) 2.00

has only 3 decimal places.

(b) C6H4O4 = 6(12.010 7) + 4(1.007 94) + 4(15.999 4) = 140.093 6
(The fourth-decimal place in the atomic mass of C has an uncertainty of 8
and the fourth-decimal place of O has an uncertainty of 3. These uncertainties are large enough to make the fourth-decimal place in molecular mass
of C6H4O4 insignificant. Therefore, another good answer is 140.094.)
(b) 75.5
(f) 11.9

(c) 5.520 103

(g) 4.600

3-7.

(a) 12.3
(e) 3.04 10-10

(d) 3.04
(h) 4.9 10-7

3-9.

All measurements have some uncertainty, so there is no way to know the true
value.

3-10. Systematic error is always above or always below the true value if you make
replicate measurements. In principle, you can find the source of this error and
eliminate it in a better experiment so the measured mean equals the true mean.
Random error is equally likely to be positive or negative and cannot be
eliminated. Random error can be reduced in a better experiment.
3-11.

The apparent mass of product is systematically low because the initial mass of
the (crucible plus moisture) is higher than the true mass of the crucible. The error
is systematic. There is also always some random error superimposed on the
systematic error.

3-12.

(a) 25.031 mL is a systematic error. The pipet always delivers more than it is

17

18

Chapter 3

rated for. The number 0.009 is the random error in the volume delivered.
The volume fluctuates around 25.031 by 0.009 mL.
(b) The numbers 1.98 and 2.03 mL are systematic errors. The buret delivers too
little between 0 and 2 mL and too much between 2 and 4 mL. The observed
variations 0.01 and 0.02 are random errors.
(c) The difference between 1.9839 and 1.9900 g is random error. The mass will
probably be different the next time I try the same procedure.
(d) Differences in peak area are random error based on inconsistent injection
volume, inconsistent detector response, and probably other small variations
in the condition of the instrument from run to run.
3-13.

(a) Carmen

(b) Cynthia

(c) Chastity

(d) Cheryl

3-14.

3.124 (0.005), 3.124 (0.2%). It would also be reasonable to keep an

additional digit: 3.1236 (0.0052), 3.1236 (0.17%)

3-15.

(a)

6.2 (0.2)
4.1 (0.1)
2.1 e e2 = 0.22 + 0.12 e = 0.224 Answer: 2.1 0.2 (or 2.1 11%)

(b)

9.43 (0.05)
0.016 (0.001)
0.150 88 ( %e)

9.43 (0.53%)
0.016 (6.25%)
%e = 6.272

%e2 = 0.532 + 6.252

Relative uncertainty = 6.27%; Absolute uncertainty = 0.150 88 0.062 7

= 0.009 46;
Answer: 0.151 0.009 (or 0.151 6%)
(c) The first term in brackets is the same as part (a), so we can rewrite the
problem as 2.1 (0.224) 9.43 (0.05) = 2.1 (10.7%) 9.43 (0.53%)
%e = 10.72 + 0.532 = 10.7%
Absolute uncertainty = 0.107 0.223 = 0.023 9
Answer: 0.223 0.024 (11%)
(d) The term in brackets is
6.2 (0.2) 10-3

e=

0.22 + 0.12 e = 0.224

+ 4.1 (0.1) 10-3

10.3 (0.224) 10-3 = 10.3 10-3 (2.17%)
9.43 (0.53%) 0.010 3 (2.17%) = 0.097 13 2.23% = 0.097 13 0.002 17
Answer: 0.0971 0.0022 ( 2.2%)

19

Experimental Error

3-16.

(a) Uncertainty = 0.032 + 0.022 + 0.062 = 0.07

Answer: 10.18 (0.07) (0.7%)
(b) 91.3 (1.0) 40.3 (0.2)/21.1 (0.2)
= 91.3 (1.10%) 40.3 (0.50%)/21.1 (0.95%)
% uncertainty = 1.102 + 0.502 + 0.952 = 1.54%
Answer: 174 (3) (2%)
(c) [4.97 (0.05) 1.86 (0.01)]/21.1 (0.2)
= [3.11 (0.0510)]/21.1 (0.2) = [3.11 (1.64%)]/21.1 (0.95%)
= 0.147 (1.90%) = 0.147 (0.003) (2%)
(d)

2.016 4
1.233
+ 4.61
7.8594

(0.000 8)
(0.002)
(0.01)
(0.000 8)2 + (0.002)2 + (0.01)2 = 0.0102

Answer: 7.86 (0.01)(0.1%)

(e)

2 016.4 (0.8)
+ 123.3 (0.2)
+ 46.1 (0.1)
2 185.8 (0.8)2 + (0.2)2 + (0.1)2 = 0.8
Answer: 2 185.8 (0.8) (0.04%)

(f) For y = xa, %ey = a%ex

x = 3.14 0.05 %ex = (0.05 / 3.14) 100 = 1.592%
1

%ey = 3 (1.592%) = 0.531%

Answer: 1.4643 0.0078 (0.53%)
ex
(g) For y = log x, ey = 0.434 29 x

0.05
x = 3.14 0.05 ey = 0.434 29 3.14 = 0.006 915

Answer: 0.4969 0.0069 ( 1.39%)

3-17.

0.001 1
1
(a) y = x1/2 %ey = 2 100 3.141 5 = 0.017 5%

(1.75 10-4) 3.141 5 = 3.1 10-4

Answer: 1.772 43 0.000 31

0.001 1
(b) y = log x ey = 0.434 29 3.141 5 = 1.52 10-4

Answer: 0.497 14 0.000 15

20

Chapter 3

(c) y = antilog x = 10x ey = y 2.302 6 ex

= (103.141 5)(2.302 6)(0.001 1) = 3.51 Answer: 1.3852 0.0035 103
0.001 1
(d) y = ln x ey = 3.141 5 = 3.5 10-4

Answer: 1.144 70 0.000 35

1 0.006
(e) Numerator of log term: y = x1/2 ey = 2 0.104 100 = 2.88%

0.3225 2.88%
0.3225 2.88%
=
0.0511 0.0009
0.0511 1.76%

= 6.311 3.375% = 6.311 0.213

ex
0.213
For y = log x, ey = 0.434 29 x = 0.434 29 6.311 = 0.015

Answer: 0.800 0.015

3-18.

(a) Standard uncertainty in atomic mass is equal to the uncertainty listed in the
periodic table divided by 3 because atomic mass has a rectangular
distribution of values.
Na = 22.989 769 28 0.000 000 02/ 3 g/mol
Cl = 35.453
0.002/ 3 g/mol
______________________________________________________________________________________

58.442 770
[(2 10-8)2]/3 + [(2 10-3)2]/3 = 1.2 10-3
58.443 0.0012 g/mol
mol
[2.634 (0.002)g] / [58.443 (0.0012)g/mol]
(b) molarity = L =
0.100 00 (0.000 08) L
=

2.634 (0.076%) / [58.443 (0.002 1%)

0.100 00 (0.08%)

relative error = (0.076%)2 + (0.002 1%)2 + (0.08%)2 = 0.11%

molarity = 0.450 7 (0.000 5) M

3-19.

da

m' 1 d
w

m =
da
1 d

0.001 2(0.000 1) g/mL

[1.034 6 (0.000 2) g] 1

8.0 (0.5) g/mL

m =
0.001 2(0.000 1) g/mL
1 0.997 299 5 g/mL

21

Experimental Error

0.001 2 (8.33%)
[1.034 6 (0.019 3%)] 1 8.0 (6.25%)

m =
0.001 2 (8.33%)
1 0.997 299 5 (0%)
m =

[1.034 6 (0.019 3%)][1 0.000 150 (10.4%)]

[1 0.001 203 (8.33%)]

m =

[1.034 6 (0.019 3%)] [1 0.000 150 (0.000 015 6)]

[1 0.001 203 (0.000 100)]

m =

[1.034 6 (0.019 3%)] [0.999 850 0 (0.000 015 6)]

[0.998 797 (0.000 100)]

m =

[1.034 6 (0.019 3%)] [0.999 850 0 (0.001 56%)]

[0.998 797 (0.010 0%)]

m = 1.035 7 (0.021 8%) = 1.035 7 (0.000 2) g

3-20.

0.2774 0.0018 g
0.2774
0.0018
=

159.688 g/mol
159.688 159.688
= 1.7371 0.0113 mmol Fe2O3;
mass of Fe = 2[1.7371 (0.0113) 10-3 mol][55.845 g/mol] = 0.19402 0.00126 g
mass of Fe per tablet = (0.19402 0.00126 g)/12 = 16.168 0.105 mg

mol Fe2O3 =

= 16.2 0.1 mg
3-21.

mol H+ = 2 mol Na2CO3

0.967 4 (0.000 9) g
0.967 4 (0.093%) g
mol Na2CO3 = 105.988 4 (0.000 7) g/mol = 105.988 (0.000 66%) g/mol
= 0.009 127 4 (0.093%) mol
mol H+ = 2(0.009 127 4 (0.093%)) = 0.018 255 (0.093%) mol
(Relative error is not affected by the multiplication by 2 because mol H+
and uncertainty in mol H+ are both multiplied by 2.)
0.018 255 (0.093%) mol
0.018 255 (0.093%) mol
molarity of HCl = 0.027 35 (0.000 04) L = 0.027 35 (0.146%) L
= 0.66746 (0.173%) = 0.667 46 (0.001 155)
= 0.667 0.001 M

3-22.

To find the uncertainty in co3, we use the function y = xa in Table 3-1,

where x = co and a = 3. The uncertainty in co3 is
0.000 000 33
%ey = a %ex = 3 5.431 020 36 100 = 1.823 10-5%
So co3 = (5.431 020 36 10-8 cm)3 = 1.601 932 796 0 10-22 cm3 with a

22

Chapter 3

relative uncertainty of 1.823 10-5%. We retain extra digits for now and round
off at the end of the calculations. (If your calculator cannot hold as many digits
as we need for this arithmetic, you can do the math with a spreadsheet set to
display 10 decimal places.)
The value of Avogadro's number is computed as follows:
mSi
28.085 384 2 g/mol
NA =
=
3
(2.329 031 9 g/cm3 1.601 932 7960 10-22 cm3)/8
(co )/8
= 6.022 136 936 1 1023 mol-1
The relative uncertainty in Avogadro's number is found from the relative
uncertainties in mSi, , and co3. (There is no uncertainty in the number 8
atoms/unit cell.)
percent uncertainty in mSi = 100 (0.000 003 5/28.085 384 2) = 1.246 10-5%
percent uncertainty in = 100 (0.000 001 8/2.329 031 9) = 7.729 10-5%
percent uncertainty in co3 = 1.823 10-5% (calculated before)
percent uncertainty in NA =
=

%emSi2 + %er2 + (%eco3)2 =

(1.246 10-5)2 + (7.729 10-5)2 + (1.823 10-5)2 = 8.038 10-5%

The absolute uncertainty in NA is (8.038 10-5%)(6.022 136 936 1 1023)/100

= 0.000 004 841 1023. Now we will round off NA to the second digit of its
uncertainty to express it in a manner consistent with the other data in this
problem:
NA = 6.022 136 9 (0.000 004 8) 1023 or 6.022 136 9 (48) 1023
3-23.

C: 12.010 7 0.000 8/ 3; H: 1.007 94 0.000 07/ 3

O: 15.999 4 0.000 3/ 3; N: 14.006 7 0.000 2/ 3
+9C:
+9H:
+6O:
+3N:
C9H9O6N3:

9(12.010 7 0.000 46)

9(1.007 94 0.000 040)
6(15.999 4 0.000 17)
3(14.006 7 0.000 12)

=
=
=
=

108.096 3 0.004 2
9.071 46 0.000 36
95.996 4 0.001 0
42.020 1 0.000 35
255.184 26 ?

Uncertainty = 0.004 22 + 0.000 362 + 0.001 02 + 0.000 352 = 0.004

Answer: 255.184 0.004

Experimental Error

3-24.

Relative uncertainties:
Large volume: 0.000 5 L/5.013 82 L = 0.010%
Small volume: 0.000 9 mL/3.793 0 mL = 0.024%
Pressure: 0.03 mm/400 mm = 0.008%
Temperature: 0.03 K/300 K = 0.01%
The largest uncertainty is in the volume of the small vessel = 0.024%.
Uncertainty in CO2 0.024% of 400 ppm = 0.000 24 400 ppm = 0.1 ppm.

23