Fundamentals of

Analytical
Chemistry Eighth Edition
CHAPTER

Using Spreadsheets in
Analytical Chemistry
Figure 3-1 The opening window in Microsoft Excel.
Note the location of the menu bar, the toolbars, the
active cell, and the mouse pointer. Chapter3 p56
 Figure 3-2 The appearance of the worksheet
after entering the labels. Chapter3 p57
Figure 3-3
Changing the column width. (a) Place the
mouse pointer on the boundary between
column A and column B, and drag to the
right to the position shown in (b).

Chapter3 p57
Chapter3 p57
Figure 3-4
Sample data entry.
Chapter3 p58
Figure 3-5
Using the fill handle to copy formulas into adjacent cells of a
spreadsheet. In this example, we clicked on cell B5, clicked on
the fill handle, and dragged the rectangle to the right to fill cells
C5 and D5. (B5 = B3-B4)
The formulas in cells B5, C5, and D5 are identical, but the cell
references in the formulas refer to data in columns B, C, and D,
respectively.
Figure 3-6
Entering the data into the spreadsheet in preparation for
calculating the mass of dry silver chloride in the crucibles.
Figure 3-7 Completing the calculation of percent chloride.
Type the formula in cell B11, click on the fill handle, and drag
to the right through cell D11.
 http://www.chem.qmul.ac.uk/iupac/AtWt/

IUPAC Commission on Atomic Weights and Isotopic Abundances.

ATOMIC WEIGHTS OF THE ELEMENTS 2005
Figure 3-8 Option window for the Edit/Paste Special…
command in Excel.
Chapter3 p61
Figure 3-9
Table of atomic weight data fro the
IUPAC Web site pasted into Excel as
HTML (hypertext markup language).
The table is highlighted and somewhat
hard to read because it has not yet been
formatted in Excel.

Chapter3 p56
Chapter3 p62
Figure 3-10
Formatted IUPAC table of atomic weights.

Chapter3 p62
Find (*) and Replace with box blank

Chapter3 p63
FIND function
FIND function = FIND(“(“, D2:D10)

Figure 3-11
Worksheet showing the results of using the FIND function
to locate the position of the left parenthesis in each of the
atomic masses of cells D2 through D10.
Chapter3 p65
VLOOKUP(“mass”, A1:B5, 2, FALSE)

FALSE是指要嚴格比對，欄位相要全部符合，不然就顯示#N/A
Chapter3 p66
Figure 3-15
Calculation of the molar mass of NaCl. The
worksheet is general for binary compounds. Type
the symbol for the first element in cell G1 and the
number of atoms of the element in H1. type the
symbol and the number of atoms of the second
element in G2 and H2. The molar mass of the
compound is displayed in cell J4.

Chapter3 p56
Mass = H2 * I2
J4 = J2 + J3

Chapter3 p68
 Fundamentals of

Analytical
Chemistry Eighth Edition
CHAPTER

Calculations Used in
Analytical Chemistry
For more than a
century, the
kilogram has
been defined as
the mass of a
single platinum-
iridium standard
housed in a
laboratory in
Sevres, France.

Chapter 4 p72
For more than a century, the kilogram has been
defined as the mass of a single platinum-iridium
standard housed in a laboratory in Sevres, France.
Meter, which is defined to be the distance that light
travels in 1/299792458 of a second (1 / 3x108).
A worldwide consortium of metrologists is working
on determining Avogadro’s number to 1 part in 100
million (0.00000001), and this number may then be
used to define the standard kilogram as 1000/12 of
Avogadro’s number of carbon atoms.
Mole=The number of atoms in 12 grams of carbon-12 (12C), an isotope of carbon
= Avogadro number.
Chapter 4 p72
mole

p64
64g copper beds 27g aluminum foil 207g lead shot

32g sulfur 52 g chromium 24 g magnesium

powder chunks chips
Approximately one mole of each of several
different elements.
Clockwise from the upper left we see 64g of
copper beds 27g of crumpled aluminum foil,
207g of lead shot, 24g of magnesium chips, 52g
of chromium chunks, and 32g of sulfur power,
The beakers in the photo have a volume of 50
mL.

Chapter 4 p74
The millimole = 10-3 mol
Molar Concentration, Cx (no. mol solute/no. L solution),
whose unit is molarity, M.
Analytical molarity = gives the total number of moles of a
solute in I L of the solution (formal concentration).
Ex. A sulfuric acid sol’n that has an anal. conc. of 1.0
M can be prepared by dissolving 1.0 mol of
sulfuric acid in water and diluting to exactly 1.0 L.
Equilibrium molarity = expresses the molar concentration
of a particular species in a solution at equilibrium
Ex. The species molarity of H2SO4 in a solution with
an anal. conc. of 1.0 M is 0.0 M because the
sulfuric acid is entirely dissociated into a mixture
of H+, HSO4-, and SO42-
Equilibrium molarity: [H2SO4]=0.00M [H+]=1.01M,
[HSO4-]=0.99M, [SO42-]=0.01M
International System of Units (SI) –
a standardized system of units

This system is based on the seven fundamental

base units (Table 4-1)

Numerous other useful units, such as volts, hertz,

Coulombs, and joules, are derived from these
base units
Numerous other useful units, such as volts, hertz (s -1), coulombs
(As), and joules, are derived from these base units

Chapter 4 p72
Mass vs. Weight

Mass, m, is an invariant measure of the amount of

Matter.

Weight, w, is the force of gravitational attraction

between that matter and Earth

Ex, a crucible weighs less in Denver than in Atlantic city

(both cities are at approx. the same latitude) because the
attractive force b/w crucible and the earth is smaller at the
higher altitude of Denver
Photo of Edwin “Buzz” Aldrin taken
by Neil Armstrong in July 1969.
Armstrong’s reflection may be seen in
Aldrin’s visor. The suits worn by
Armstrong and Aldrin during the
Apollo 11 mission to the Moon
appear to be massive. But because the
mass of the Moon is only 1/81 that of
Earth and the acceleration due to
gravity is only 1/6 that on Earth, the
weight of the suits on the Moon was
only 1/6 of their weight on Earth. The
mass of the suits, however, was
identical in both locations.

Chapter 4 p73
Chapter 4 p72
Ex 4-1 how many moles and millimoles of benzoic
aicd (M=122.1 g/mol) are contained in 2.00 g of the
pure acid?

Molecular model of benzoic acid,

C6H5COOH. Benzoic acid occurs
widely in nature, particularly in
berries. It finds broad use as a
preservative in foods, fats, and
fruit juices; as a mordant for
dying fabric; and as a standard in
calorimetry and in acid/base
analysis.
Chapter 4 p72
Ex 4-4 Calculate the analytical and equilibrium molar
concentrations of the solute species in an aqueous
solution that contains 285 mg of trichloroacetic acid (163.4
g/mol), in 10.0 mL (the acid is 73% ionized in water)?

Molecular model of trichloroacetic acid (TCA), Cl3CCOOH

Chapter 4 p78
Molecular model of trichloroacetic acid (TCA),
Cl3CCOOH. The rather strong acidity is usually
ascribed to the inductive effect of the three chlorine
atoms attached to the end of the molecule opposite
the acidic proton. Electron density is withdrawn away
from the carboxylate group so that the
trichloroacetate anion that is formed when the acid
dissociates is stabilized. The acid is used in protein
precipitation and in dermatological preparations for
the removal of undesirable skin growths.
Amount HA = 285 mg HA/1000  163.4 = 1.744 x 10-3 mole HA
Analytical molar concentration,
CHA = 1.744 x 10-3 mole HA / 10 mL x 1000 = 0.174 M
As for equilibrium molar concentrations of the solute species, in this
solution, 73% of the HA dissociates, giving H+ and A-

HA  H+ + A-

[HA] = CHA x (100-73)/100 = 0.174 M x 0.27 = 0.47 mol/L

The species molarity of A- is equal to 73% of the analytical concentration

of HA.

[A-] = 73 mol A- / 100 mol HA x 0.174 mole HA/L = 0.127 M

[H+] = [A-] = 0.127 M
Percent Concentration
weight percent (w/w) = weight solute/weight sol’n x 100%
Volume percent (v/v) = volume solute/volume sol’n x 100%
Weight/volume percent (w/v) =
weight solute, g/volume solution, mL x 100%

Parts per Million and Parts per Billion

cppm = mass of solute / mass of solution x 106 ppm
cppb = mass of solute / mass of solution x 109 ppb
cppt = mass of solute / mass of solution x 103 (parts per thousand)
or 1012 (parts per trillion)

p-Functions or p-value
pX = -log[X]
Density
expresses the mass of a substance per unit volume.
In SI units, density is expressed in units of kg/L or g/mL.

Specific density
is the ratio of the mass of a substance to the mass of
an equal volume of water
Figure 4-1
Label from a bottle of reagent-grade
hydrochloric acid. Note that the specific gravity
of the acid over the temperature range of 60°
to 80° F is specified on the label (Label
provided by Mallinckrodt Baker, Inc.,
Phillipsburg, NJ 08865).

Chapter 4 p82
 Molecular model of HCl.
Hydrogen chloride is a gas
consisting of heteronuclear
diatomic molecules. The gas
is extremely soluble in water,
when a solution of the gas is
prepared, only then do the
molecules dissociate to form
aqueous hydrochloric acid,
which consists of H3O+ and
CI- ions.

Chapter 4 p81
 is the ratio of the mass of a substance
to the mass of an equal volume of
water

12 M

16 M

18 M

1.19 x 103 x 37.2 / (100 x 36.5) = 12.12 M

1.42 x 103 x 70.5 / (100 x 63.0) = 15.89 M
Chapter 4 p82
Figure 4-2
Flow diagram for making stoichiometric calculations. (1)
When the mass of a reactant or product is given, the
mass is first converted to the number of moles, using
the molar mass. (2)The stoichiometric ratio given by
the chemical equation for the reaction is then used to
find the number of moles of another reactant that
combine with the original substance or the number of
moles of product that form. (3) Finally, the mass of the
other reactant or the product is computed from its
molar mass.

Chapter 4 p84
Chapter 4 p84
 Fundamentals of

Analytical
Chemistry Eighth Edition
CHAPTER

Errors in Chemical
Analyses
Error has two different meanings:

(1)The difference between a measured value and the

“true” or “known” value.

(2) The estimated uncertainty in a measurement or

experiment.
Montparnasse Station in Paris
October, 1895
Measurements involve errors and
uncertainties, caused by faulty calibrations
or standardization or random variations and
uncertainties
Figure 5-1
Results from six replicate determinations of
iron in aqueous samples of a standard
solution containing 20.0 ppm iron (III)

Chapter 5 p91
Results from 6 replicate determinations of iron in aqueous samples
of a standard solution containing 20.0 ppm iron

Measurement uncertainties cause replicate results to vary

Replicates – are samples of about the same size that
are carried through an analysis in exactly the same
way

Mean – average of 2 or more measurements

Median – the middle value in a set of data that has

been arranged in numerical order

Outlier – a result that differs significantly from

others in the set, which can have significant effect
on the mean of the set but has no effect on the median.
Ex 5-1 Calculate the mean and median for the
data shown in Figure 5-1

19.4, 19.5, 19.6, 19.8, 20.1, 20.3

Mean = Sum of data / 6 = 19.78  19.8 ppm
Median = (19.6 + 19.8) / 2 = 19.7 ppm
Deviation from the mean =  Xi – mean 
Precision vs. Accuracy
Figure 5-2
Illustration of accuracy and precision using the pattern
of darts on a dartboard. Note that we can have very
precise results (upper right) with a mean that is not
accurate, and an accurate mean (lower left) with data
points that are imprecise.

Chapter 5 p93
Chapter 5 p91
Precision – the closeness of results to other obtained
in exactly the same way

Accuracy – the closeness of a measured value to the

true or accepted value

Absolute error – a measurement is the difference b/w

measured value and the true value.

Relative error – more useful quantity than absolute

 Ex 5-1 Calculate the mean and median for the
data shown in Figure 5-1

Deviation from the mean =  Xi – mean 

19.4, 19.5, 19.6, 19.8, 20.1, 20.3

Mean = Sum of data / 6 = 19.78  19.8 ppm
Median = (19.6 + 19.8) / 2 = 19.7 ppm
Deviation from the mean =  Xi – mean 
Absolute error = Xi – Xt (true value or accepted value of the quantity)
Relative error = (Xi – Xt )/ Xt x 100%
Figure 5-3
Absolute error in the micro-Kjeldahl determination of
nitrogen (benzyl isothiourea hydrochloride and nicotinic
acid). Each dot represents the error associated with a
single determination. Each vertical line labeled (χi-χt) is the
absolute average deviation of the set from the true value.
(Data from C. O. Willits and C. L. Ogg, J. Assoc. Offic. Anal.
Chem., 1949, 32, 561. With permission.)

Chapter 5 p94
Chapter 5 p94
So called niacin, occur
in all living cells, and it is
essential in the nutrition
of mammals. It is used in
the prevention and
treatment of pellagra.

Chapter 5 p94
relatively high precision and high accuracy

poor precision but good accuracy

excellent precision, but error occurs

both precision and accuracy are poor

Chapter 5 p94
Three types of errors occur in chemical analyses
(1) Random (or indeterminate) error
Causes data to be scattered more or less symmetrically
around a mean value (affect measurement precision)
(2) Systematic (or determinate) error
Causes the mean of a data set to differ from accepted
value (affect the accuracy of results)
(3) Gross error
Differ from (1) and (2), the product of human error,
only occur occasionally
Systematic errors~
(1)Have a definite value and an assignable cause
(2)Of the same magnitude for replicate measurements
(3)May lead to bias in measurement results (affect all
of the data in a set in the same way)
(4) Sources
a. Instrumental errors
Caused by nonideal instrument behavior, by
faulty calibration, or by use under inappropriate
conditions
Can be found and corrected by calibration.
Periodic calibration of equipment is always
desirable
b. Method errors
Arise from nonideal chemical or physical
behavior of analytical systems
Most difficult to identify and correct

c. Personal errors
Resulted from the carelessness, inattention or
personal limitations
Systematic errors
(1) May be constant or proportional
(2) Constant errors are independent of the size of the
sample being analyzed
ex becomes more serious as the size of the quantity
measured decreases
(3) Proportional errors decrease or increase in
proportion to the size of the sample
ex, the presence of interfering contaminants
Detection of systematic method errors
(1)Bias in an analytical method is particularly
difficult to detect
(2) How?
a. Analysis of Standard Samples
Standard reference materials (SRMS) – sold by
NIST and certified to contain specified conc. of
one or more analytes
b. Independent Analysis
A second independent and reliable analytical
method can be used in parallel with the method
being evaluated
Standard reference
materials from
NIST.

Chapter 5 p99
c. Blank Determination
A blank contains the reagents and solvents used
in a determination, but no analyte. It reveals
errors due to interfering contaminants from the
reagents and vessels.
d. Variation in Sample Size
Constant errors can often be detected by varying
the sample size