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Calculations Used in
Analytical Chemistry
Fundamentals of Analytical Chemistry, 10e – Skoog
Analytical Chemistry, 7e - Christian
Terminologies
• Solution – homogeneous mixture of 2 or more substances
• Solute – minor
• Solvent – major
• Concentration – states how much solute is contained in a given
volume or mass of solution
• Electrolyte
• Weak – partially dissociated into ions in a solution
• Strong – fully dissociated into ions in a solution
Electrolytes
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Terminologies
• The molar analytical concentration, or analytical concentration, of
a solution gives the total number of moles of a solute in 1 L of the
solution (or the total number of millimoles in 1 mL).
Terminologies
• The molar equilibrium concentration, or just equilibrium
concentration, refers to the molar concentration of a particular
species in a solution at equilibrium.
• To specify the molar equilibrium concentration of a species, it is
necessary to know how the solute behaves when it is dissolved in a
solvent.
Example
Calculate the analytical and equilibrium molar concentrations of the solute species in an aqueous
solution that contains 285 mg of trichloroacetic acid, "# ""$$% (163.4 g/mol), in 10.0 mL (the acid
!
is 73% ionized in water).
Solution
As in Example 2-3, we calculate the number of moles of
"#!""$$%C which we designate as HA,
and divide by the volume of the solution, 10.0 mL, or 0.0100 L. Therefore,
/ .)!" /A%2)!"
#A%&'()!" * !!" * H,- A.)!" 0 0
/111 A.)!" /3456 .)!"
!4
* /57660/1 A%2)!"
The molar analytical concentration, #!" ! is then
A%&''(A) !! *H,-"# A))) *L *H,-"#
!"# . ( . )%A&' . )%A&'-M
A)%) *L AL L
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Example
In this solution, 73% of the HA dissociates, giving #!A%&'( " )
The equilibrium concentration of HA is then 27% of !!" # Thus,
[!" ] = !!" ! (#AA " %& ) ' #AA = A(#%) ! A(*% = A(A)%H,-.'L = HA(A)%HM
The equilibrium concentration of ! ! is equal to 73% of the analytical concentration of HA, that is,
!"#A%&' ! #A%H'
$" ' %# ( )** #A%H' ,*-)!.
!
( *-)L!M
1
Because 1 mole of "! is formed for each mole of ! ! " we can also write
!"+ ] = #A[ % ! & = '()*HA,
and
#!" = [!" ] + #" ! A = %&%'( + %&)*( = %&)('H,
SI Units
• Scientists throughout the world have adopted a standardized system of units
known as the International System of Units (SI). This system is based on the
seven fundamental base units shown in Table 2-1 (SI Base Units).
S I B ase U nits
P hysical Q uantity N am e of U nit A bbreviation
M ass kilogram kg
Length m eter m
Tim e second s
Tem perature kelvin K
A m ount of substance m ole m ol
E lectric current am pere A
Lum inous intensity candela cd
SI Units
To express small or large measured quantities
in terms of a few simple digits, prefixes are
used with these base units and other derived
units. As shown in Table 2-2, these prefixes
multiply the unit by various powers of 10.
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The Distinction Between Mass and Weight
• Mass is an unchanging measure of the quantity of matter in an object.
Weight is the force of attraction between an object and its surroundings,
principally Earth. Because gravitational attraction varies with geographical
location, the weight of an object depends on where you weigh it.
• Weight and mass are related by the familiar expression below.
w = mg
• In this expression, w is the weight of an object, m is its mass, and g is the
acceleration due to gravity.
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The Mole
• The mole (abbreviated mol) is the SI unit for the amount of a chemical substance.
• It is always associated with specific microscopic entities such as atoms, molecules,
ions, electrons, other particles, or specified groups of such particles as represented
by a chemical formula. One mole contains exactly #$%!!&'%(#)&%!"$
elementary entities (atoms, molecules, ions, electrons, and so on).
• The fixed number #$%!!&'%(#)&%!" is known as Avogadro’s constant.
• When expressed in the unit mol−1, this number is called Avogadro’s number,
which is often rounded to #$%!!&'%!"$
• The molar mass M of a substance is the mass in grams of 1 mole of that
substance.
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The Millimole
• Sometimes it is more convenient to make calculations with
millimoles (mmol) rather than moles.
• The millimole is 1/1000 of a mole.
• The millimolar mass (mM) is 1/1000 of the molar mass.
" #$%%&'$($#) !! %&'
" #$! %&&'(%)%# &'(
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Example
Find the number of moles and millimoles of benzoic acid (M = 122.1 g/mol) that are
contained in 2.00 g of the pure acid.
Solution
If we use HBz to represent benzoic acid, we can write that 1 mole of HBz has a mass of 122.1
g. Therefore,
/B&0!!"#
$B&'() !!"# * !!"# * H,-- .!!"# 1 (2-1)
/HH,/ .!!"#
* -,-/23B&0!!"#
To obtain the number of millimoles, divide by the millimolar mass (0.1221 g/mmol), that is,
/!""#0!'()
!"#$B& !'() * H,-- .!'() 1 * /2,3 !""#0!'()
-,/HH/ .!'()
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Example
What is the mass in grams of #$ + ( !!%&& ' ()* ) +,-+!.%/ '+)0+#$ NO (3?!%/ ' ()* ) 4
! ?
Solution
The chemical formula indicates that 1 mole of Na 2SO 4 contains 2 moles of Na +, that is,
"&'-$%!
%&'()*+$%! , !$%! , &'-+$% "./ # 0
&'-$%"./ #
To find the number of moles of Na 2SO 4, proceed as in Example 2-1:
O'(3#$!%& "
$'()*+#$!%& " , !#$!%&" , !-./ 0N#$ !%& " 4
O"!./ 0#$!%& "
Combining this equation with the first leads to
3 &'4+$%"NO # "&'4$%!
%&'()*+$%! , !$%! , "-./ 0+$% "NO # 5 5
3#"./ 0+$%"NO # &'4+$%"NO #
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Example
To obtain the mass of sodium in 25.0 g of #$!%&" ' multiply the number of moles of
"#! by the molar mass of "#! , or 22.99 g. And so,
**+,, -%&#!
"#$$%&#! ' "()%&#! .
"()%&#!
Substituting the previous equation gives the mass in grams of "#! $
0 $NO'(%"./ # " $NO(%! ""+44 -(%!
$%&&'(%! ) "*+, -'(% "./ # 3 3 3
0#"+, -'(%"./ # $NO'(%"./ # $NO(%!
) 5+0, -(%!
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Concentrations of Solutions
• The molar concentration " ! of a solution of a solute species X is the
number of moles of that species that is contained in 1 L of the solution (not 1 L
of the solvent).
• Equation 2-2 describes the molar concentration in terms of the number of
moles of solute (n) and the volume (V) of solution,
!!
"" #
# (2-2)
$%&'(%)*+ !+%),-*
(%)./ !0%$0*$-/.-1%$ #
2%),(* !1$!)1-*/+
§ The unit of molar concentration is molar, symbolized by M, which has the
dimensions of "#$ % &'(#)("#$(&!!*
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Example
Calculate the molar concentration of ethanol in an aqueous solution that contains 2.30 g of
#!$"%$ ( C'()C * H,- ) in 3.50 L of solution.
Solution
To calculate molar concentration, we must find both the amount of ethanol and the volume of the
solution. The volume is given as 3.50 L, so all we need to do is to convert the mass of ethanol to the
corresponding amount of ethanol in moles.
O'(3,#!$"%$
C'()*H,#!$"%$ - !#!$"%$ - !./0 1,#!$"%$ 4
56.07 1,#!$"%$
- 0.0588!!'(3!#!$"%$,
To obtain the molar concentration, !# $ %$ C divide the amount by the volume. Thus,
! "
,-.L*#!$"%$
!C'( )*#!$"%$ M
1OC(3 )*#!$"%$
!#!$"%$ H
'C"(4
H (C(,1'-.L*#!$"%$ 5 4 H (C(,1'*6
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Preparation of Solution of Specified Molarity
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Normality
Normality (N)
&,$)-.#&L% "' !"#$%&
2"N3.#)%4 " 2 ! =
0)%&N "' !"#$%)"L
(&)*+% "' !"#$%&
&,$)-.#&L% "' !"#$%& =
&,$)-.#&L% (&)*+% "' !"#$%&
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Equivalent Weight
• Weight of substances that are equivalent to one another
in chemical reaction.
• The equivalent of an oxidizing agent or reducing agent is
the weight of the substance required to gain or lose 1
mole of electron.
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Equivalent Weight
Equivalent Weight = molecular weight (MW)
f (factor)
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Reacting Capacity of Solute
ACID BASE SALT
f Total number Total number Total (+/-)
of H+ of replaceable charge
replaceable OH-
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Relationship between Normality and
Molarity
N= n solute xf
liter of solution
N = molarity (M) x f
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Dilution
• If the concentration needed in an experiment is less than the
specified molarity, dilution is needed rather than trying to make
another solution.
• Dilution is a procedure for preparing a less concentrated solution
from a concentrated one.
• Number of moles per solute is not altered by addition of a solvent
#! $! %&#" $"
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Example
• Copper sulfate is widely used as a dietary supplement for animal
feed
• A lab technician prepares a stock solution of CuSO4 by adding 40.00 g of
CuSO4 to enough water to make 500.0 mL of solution
• An experiment requires a 0.1000 M solution of CuSO4
• Find the molarity of the CuSO4 stock solution prepared
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Example
• Solution
• Calculating
"#$%C
!'(''#)##*+,-! ##.# #/#'(01'O#$%C
"13(O#)
• Calculating Mstock solution
!"#$!%&'()
& &*&!"$!+,&-
!"$!!!&.
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Mole Fraction
• Represented by the symbol X
• Mole fraction of A is the number of moles of A divided by the total number
of moles in the solution
%#&'()! A
* ! +) )+) !
"#",&)%#&'( A
• Mole fractions of all components must add"#"to unity
# ! ABA# " ABA&&&A'A(
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Example #2
• Hydrogen peroxide is used by some water treatment
systems to remove the disagreeable odor of sulfides in
drinking water. It is available commercially in a 30.0% by
mass aqueous solution
• What is the mole fraction of H2O2?
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Example
• Take a basis: 100 g of solution
• Since the problem states that 30% by mass solution is available,
by assuming there is 100 g of the solution we can get 30 g of
hydrogen peroxide and 70g of water.
• Calculating the number of moles
• Moles in H2O "#$# !
$" !# %&% ,($#!%-.)*+ %&%'$((%)*+
• Moles in H2O2
"#$# !
$" !# ! %&% "+$#!%,-()* %&%#$''!%()*
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Example #2
• Total number of moles
%!"! "#"%# !$ ! "$"%# !$ "
"""""#"%&''!"()*"$"+&''"()*"#",&-."()*
• The mol fraction of hydrogen peroxide
%! !" ! #$%%!"&'(
&! !" ! "")" ")"
%#$# *$+,"&'(
"""""""""")"#$-%.
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Mass Percent
• Percent by mass (also called percent by weight or weight
percent) is the ratio of the mass of a solute to the mass of the
solution, multiplied by 100 percent.
mass solute
%𝑏𝑦𝑚𝑎𝑠𝑠 = × 100%
total mass solution
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Example
• A solution is prepared by dissolving 24g of NaCl in 152 g of
water. What will be the percent by mass of NaCl in the
resulting solution?
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Example #3
!"#
$%CC#'()*(+,#-.#/%MN#2## #3#4556
!"#7 849!#7#
!"
####################################2# #3#4556#2#4"6
4:;
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Part per million
• Parts per million or ppm is the defined as amount of
solute in a million amount of solution.
𝑚𝑎𝑠𝑠 𝑠𝑜𝑙𝑢𝑡𝑒
𝑝𝑝𝑚 = 𝑥10!
𝑚𝑎𝑠𝑠 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑣𝑜𝑙𝑢𝑚𝑒 𝑠𝑜𝑙𝑢𝑡𝑒
𝑝𝑝𝑚𝑣 = 𝑥10!
𝑣𝑜𝑙𝑢𝑚𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
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Parts per million
• For very dilute solutions, the density of the substance is
almost the same as that of the solvent (water)
• Example: a drop of salt in 1 L water
• ppm can be expressed as,
𝑚𝑔 𝑠𝑜𝑙𝑢𝑡𝑒
𝑝𝑝𝑚 =
𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
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Molality
• Molality is the number of moles of solute dissolved in every kg of a
solvent. The units of molality is mol/kg (molal) or simply m.
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑚=
𝑘𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
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Example
• Glucose, C6H12O6, in water is often used for intravenous feeding
• Sometimes sodium ions are added to the solution
• A pharmacist prepares a solution by adding 2.0 mg of sodium ions (in the
form of NaCl), 6.00 g of glucose, and 112 g of water
• Determine the molality of the glucose in solution
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Example #4
• Calculating the moles of solute
!"##$%$%&'()*+
,)&+*$*)&'-+$.%&'()*+/$0$ $
12#"1!$% 3 ,)&
$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$0$#"#444$
• Calculating the mass of solvent
""!#$
%&'()#&* #)&'H(,-#./!01#O,#3$#4# #
"555
##############################################4#56""!#
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Example
• Calculating m
"#$%&'#( ')$*H#&%
"#$%&'',' '
-)'.!/
010OOO
''''''''''',' '
0133!'-)
''''''''''','01!45'"
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Density and Specific Gravity
• Density – mass of substance/volume of the substance
• g/mL, kg/L
• Specific gravity – ratio of density of a substance relative to another
fluid
• Dimensionless
• Example:
• Calculate the molar concentration of nitric acid (63 g/mol) in a
solution that has a specific gravity of 1.42 and is 70.5% (w/w) nitric
acid
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Conversion of Concentration Units
• Sometimes it is desirable to convert one concentration unit of a
solution to another
• Taking a basis will make the calculations easier
• For molarity to be converted to another concentration unit, the
density of the solution must be present. Remember that molarity is
mol/L, we need to convert the L of solution to a mass solution.
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Conversion of Concentration Units
Concentration unit Basis
Mass Percent 100 g of solution
Molarity 1 L solution
Molality 1000 g or 1 kg solvent
Mole fraction 1 mole of solution
ppm 1,000,000 g solution, 1,000,000 L
solution, or 1 L solution
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Conversion of Concentration Units
• Why use those as a basis?
• The answer is simple. The given value for that concentration unit
will be equal to the numerator of the equation.
• Example: 30% by mass to molality
• If you assume 100 g solution,
𝑚𝑎𝑠𝑠 𝑠𝑜𝑙𝑢𝑡𝑒
30 = 𝑥100
100 𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
• The mass of solute will be equal to 30 g. From there you can now
start to convert from one unit to another.
43
Example
• The mole fraction of the solvent in an aqueous
solution of caffeine, C8H10O2N4, is 0.9. Calculate
the molality, mass percent of the solvent, and ppm
of the solute.
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Example #5
• Component A will be caffeine, Component B will be the solvent
• Since mole fraction is given, we can assume 1 mole of total
solution
• This will give us %#&'()! A
* ! +) )+) !
"#",&)%#&'( A "#"
!!
0.9 = " $%&' ; n( = 0.9 mole B, n) + n(=1
n) = 1 − n(= 0.1 mole A
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Example
• Get the mass of each component (remember Stoichiometry)
"#.%& (
• Mass of H2O (component B) = 0.9 𝑚𝑜𝑙 𝐵 𝑥 = 16.2 g
" )*+
",-.& (
• Mass of Caffeine = 0.1 𝑚𝑜𝑙 𝐴 𝑥 = 19.4 g
" )*+
46
Example #5
• For molality
0.1 𝑚𝑜𝑙
𝑚= = 6.17 𝑚
1 𝑘𝑔
16.2𝑔 𝑥
1000𝑔
• For ppm solute
19.4 𝑔
𝑝𝑝𝑚 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 = 𝑥 10. = 5.45×10/
(16.2𝑔 + 19.4𝑔)
• For mass percent of solvent
16.2𝑔
𝑚𝑎𝑠𝑠 % = 𝑥 100 = 45.5%
19.4 + 16.2 𝑔
47
p-Value or p-Function
• p-Value is the negative logarithm (to the base 10) of the molar
concentration of that species.
48
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Example
• Find the [H+] and pH of a tap water sample in which
[OH-] = 2.0 × 10-7
49
Example
• Using pOH
pOH = - log(2.0 x 10-7) = 6.6990
• Since pH + pOH = 14,
pH = 14 – pOH = 7.3010
50
Example
• Find the [H+] and [OH-] of human blood at pH 7.40
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Example
• From pH, we can solve for the concentration of H+
pH = - log(H+) = 7.40
[H+] = 10-7.40= 3.9811 x 10-8 M
• For [OH-],
pOH = 14 – 7.40 =6.6
• Using the same method in solving for H+ concentration
[OH-]=2.5119 x 10-7M
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Titer
• Used in routine volumetric analysis
• Defined as the weight of analyte that is chemically equivalent to 1
mL of the titrant, usually expressed in mg.
53
Stoichiometry
• Stoichiometry is the quantitative study of reactants and products
in a chemical reaction.
• Mole method – stoichiometric coefficients in a chemical equation
can be interpreted as the number of moles of each substance.
• REVIEW:
• Empirical formula determination
• Molecular formula determination
• Limiting and Excess Reagent Problems
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Steps in Calculating the Amounts of
Reactants and Products
[Link] the balanced chemical equation.
[Link] quantities of known substances into moles.
[Link] coefficients in balanced equation to calculate the number
of moles of the sought quantity.
[Link] moles of sought quantity into the desired units.
55
Example
• Methanol burns in air according to the equation
• 2 CH3OH + 3 O2 2 CO2 + 4 H2O
• If 209 g of methanol are used up in the combustion, what
mass of water is produced?
56
Example
4 mol H2O 18.0 g H2O
209 g CH3OH x 1 mol CH3OHx x =
32.0 g CH3OH 2 mol CH3OH 1 mol H2O
235 g of H2O
57
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Example
• Ammonia is used to make fertilizers for lawns and gardens by
reacting nitrogen gas with hydrogen gas. The balanced equation
for the reaction is
#! $%&'('")! $%& ! !#)" $%&
• How many moles of ammonia are formed when 1.34 mol of
nitrogen react?
58
Limiting Reactant and Theoretical Yield
• 2 Sb (s) + 3 I2 (s) → 2 SbI3 (s)
60
Approach to Limiting Reactant Problems
• Calculate the amount of product that will form if the first reactant
were completely consumed
• Repeat the calculation for the second reactant in the same way
• Choose the smaller amount of product and relate it to the
reactant that produced it
• This is the limiting reactant, and the resulting amount of product is the
theoretical yield
• From the theoretical yield, determine how much of the reactant in
excess is used, and subtract from the starting amount
61
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Example
• Consider the reaction
! &'( ! !#$*" &'(
What is the limiting!#$%&'(%)%"*
reactant and theoretical yield
when 1.20 mol of Sb and 2.40 mol of I2 are mixed?
62
Example
• Solution:
• mol SbI3 "#$%&#'()!
*+"I#$%&#'(#-# #.#*+"I#$%&
"#$%&#'(
"#$%&#'()!
"*+I#$%&#) " #-# #.#/*0I#$%&
!#$%&#) "
• Limiting reactant
• 1.20 mol (Sb limiting) < 1.60 mol (I 2 limiting); the limiting reactant is Sb
• Theoretical yield
• 1.20 mol < 1.60 mol; the theoretical yield is 1.20 mol SbI 3
63
Experimental Yield
• Quantity of product measured after performing the reaction in the
laboratory
• Experimental yields are always lower than theoretical yields
• Some of the product is lost to competing reactions
• Some of the product is lost to handling
• Some of the product may be lost in separating it from the reaction mixture
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Percent Yield
• Defined as #!$-!'( +%!*,./.
!"#!$%&!'()* +%!*,
01223
(4!5$!(%-)* +%!*,
65
Example
• Consider the reaction between magnesium and
iodine to produce magnesium iodide. A student
determines by calculation that with the amount of
reagents he has on hand, he should produce 1.71
mol of MgI2. After the reaction is complete, he tells
his TA that he got a yield of 84.5%. How many
grams of MgI2 did he make?
66
Example
• Solution:
!"#$!% &'(%)
*(+"(,# &'(%)-.- /0112
#3(4+(#'"!% &'(%)
• Actual yield
"#$%"& '()&*
+I-./M/1/ 2344M
3-53/67&
• Mass MgI2 "#$%"&/'()&*/1/3-II/67&/89: !
!"#$%&'&(') !
%$**&+I-&(') ! . /&*M!&'
%&+I-&(') !
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