Stoichiometric Calculations: Review of Fundamental Concepts

Stoichiometric Calculations
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1. Review of Fundamental Concepts
2. Molarity Calculations
3. Normality Calculations
4. Density Calculations
5. Analytical versus Equilibrium Concentration
6. Dilution Problems
7. Expression of Analytical Results, %, ppt, ppm, ppb
8. Volumetric Analysis Using Molarity
9. Back-Titrations
10. Volumetric Analysis using Normality
11. The Titer Concept
Review of Fundamental Concepts

Formula Weight
It is assumed that you can calculate the formula or molecular weights of compounds from
respective atomic weights of the elements forming these compounds. The formula weight (FWt)
of a substance is the sum of the atomic weights of the elements from which this substance is
formed from.
The formula weight of CaSO4.7H2O is
Element
Atomic weight
Ca
S
11 O
14 H
FWt
40.08
32.06
11x16.00
14x1.00
= 262.14
The Mole
The mole is the major word we will use throughout the course. The mole is defined as gram
molecular weight which means that:
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Mole
Grams
1 mol H2
2.00 g
1 mol O2
32.00 g
1mol O
16.00 g
1mol NaCl
1 mol Na2CO3
58.5 g
106.00 g
Assuming approximate atomic weights of 1.00, 16.00, 23.00, 35.5, and 12.00 atomic mass unit
for hydrogen, oxygen, sodium, chlorine atom, and carbon, respectively.
The number of moles contained in a specific mass of a substance can be calculated as:
mol = g substance/FWt substance
The unit for the formula weight is g/mol
In the same manner, the number of mmol of a substance contained in a specific weight of the
substance can be calculated as
mmol = mol/1000
Or,
mmol = mg substance/FWt substance
Look at this calculation
The number of mmol of Na2WO4 (FWt = 293.8 mg/mmol) present in 500 mg of of Na2WO4
can be calculated as
? mmol of Na2WO4 = 500 mg/293.8 mg/mmol = 1.70 mmol
The number of mg contained in 0.25 mol of Fe2O3 (FWt = 159.7 mg/mmol) can be calculated
as
? mg Fe2O3 = 0.25 mmol Fe2O3 x 159.7 mg/mmol = 39.9 mg
Therefore, either the number of mg of a substance can be obtained from its mmols or vice versa.
Calculations involving solutions

Molarity (M)
Molarity of a solution can be defined as the number of moles of solute dissolved n 1 L of
solution. This means that 1 mol of solute will be dissolved in some amount of water and the
volume will be adjusted to 1 L. The amount of water may be less than 1 L as the final volume of
solute and water is exactly 1 L.
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Calculations Involving Molarity

These are very simple where
Molarity = mol/L = mmol/mL
This can be further formulated as
Number of moles = Molarity X volume in Liters, or
mol = M (mol/L) x VL
Number of mmol = Molarity x volume in mL , or
mmol = M (mmol/mL) x VmL
Look at the following calculations involving molarity
Find the molarity of a solution resulting from dissolving 1.26 g of AgNO3 (FWt = 169.9 g/mol)
in a total volume of 250 mL solution.
First find mol AgNO3 = 1.26 g AgNO3 / 169.9 g/mol = 7.42x10-3 mol
Also you should know that 250 mL = 0.25 L
Now one can calculate the molarity directly from
Molarity = mol/L
M = 7.42x10-3 mol/0.25 L = 0.0297 mol/L
We can find the molarity directly in one step using dimensional analysis
? mol AgNO3 / L = (1.26 g AgNO3 / 250 mL) x ( mol AgNO3/169.9 g AgNO3) x (1000
mL/1L) =0.0297 M
Let us find the number of mg of NaCl per mL of a 0.25 M NaCl solution
First we should be able to recognize the molarity as 0.25 mol/L or 0.25 mmol/mL. Of course,
the second term offers what we need directly
? mg NaCl in 1 mL = (0.25 mmol NaCl/mL) x (58.5 mg NaCl/mmol NaCl) = 14.6 mg
NaCl/mL
A more practical problem is to calculate the weight of a substance needed to prepare a
specific volume of a solution with predefined concentration. For example
Find the number of grams of Na2SO4 required to prepare 500 mL of 0.1 M solution.
First, we find mmoles needed from the relation
mmol = M (mmol/mL) x VmL
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mmol Na2SO4 = 0.1 mmol/mL x 500 mL = 50 mmol

mmol = mg substance/FWt substance
? mg Na2SO4 = 50 mmol x 142 mg/mmol = 7100 mg or 7.1 g
One can use dimensional analysis to find the answer in one step as
? g Na2SO4 = (0.1 mol Na2SO4/1000 mL) x 500 mL x (142 g Na2SO4/mol) = 7.1 g
When two or more solutions are mixed, one can find the final concentration of each ion.
However, you should always remember that the number of moles ( or mmoles ) is additive. For
example
Find the molarity of K+ after mixing 100 mL of 0.25 M KCl with 200 mL of 0.1 M K2SO4.
The idea here is to calculate the total mmol of K+ and divide it by volume in mL.
mmol K+ = mmol K+ from KCl + mmol K+ fro K2SO4
= 0.25 mmol/ml x 100 mL + 2x0.1 mmol/mL x 200 mL = 65 mmol
Molarity = 65 mmol/(200 + 100) mL = 0.22 M
Note that the concentration of K+ in 0.1M K2SO4 is 2x0.1M (i.e. 0.2 M)
Normality
We have previously talked about molarity as a method for expressing concentration. The second
expression used to describe concentration of a solution is the normality. Normality can be
defined as the number of equivalents of solute dissolved in 1 L of solution. Therefore, it is
important for us to define what we mean by the number of equivalents, as well as the equivalent
weight of a substance as a parallel term to formula weight.
An equivalent is defined as the weight of substance giving an Avogadros number of reacting
units. Reacting units are either protons (in acid base reactions) or electrons (in oxidation
reduction reactions). For example, HCl has one reacting unit (H+) when reacting with a base like
NaOH but sulfuric acid has two reacting units (two protons) when reacting completely with a
base. Therefore, we say that the equivalent weight of HCl is equal to its formula weight and the
equivalent weight of sulfuric acid is one half its formula weight. In the reaction where Mn(VII),
in KMnO4, is reduced to Mn(II) five electrons are involved and the equivalent weight of
KMnO4 is equal to its formula weight divided by 5.
Number of equivalents = Normality x VL = (eq/L) x L
Number of milliequivalents = Normality x VmL = (meq/mL) x mL
Also, number of equivalents = wt(g)/equivalent weight (g/eq)
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Or, number of milliequivalents = wt(mg)/equivalent weight (mg/meq)

Let us not be lost by the above arguments and make concepts more practical. I think you just
need to know the following to answer any problem related to normality calculations:
Equivalent weight = FWt /n
Number of equivalents = n x number of moles
Also, N = n M
Where n is the number of reacting units ( protons or electrons ) and if you are forming factors
always remember that a mole contains n equivalents. The factor becomes (1 mol/n eq) or (n
eq/1 mol).
One last thing to keep in mind is that when dealing with normality problems always 1 eq of A
reacts with 1 eq of B regardless of the stoichiometry of the reaction since this stoichiometry was
used in the calculation of normalities.
Example
Find the equivalent weights of NH3 (FW = 17.03), H2C2O4 (FW = 90.04) in the reaction with
excess NaOH, and KMnO4 (FW = 158.04) when Mn(VII) is reduced to Mn(II).
Solution
Ammonia reacts with one proton only
Equivalent weights of NH3 = FW/1 = 17.03 g/eq
Two protons of oxalic acid react with the base
Equivalent weights of H2C2O4 = FW/2 = 90.04/2 = 45.02 g/eq
Five electrons are involved in the reduction of Mn(VII) to Mn(II)
Equivalent weights of KMnO4 = FW/5 = 158.04/5 = 31.608 g/eq
Example
Find the normality of the solution containing 5.300 g/L of Na2CO3 (FW = 105.99), carbonate
reacts with two protons.
Solution
Normality is the number of equivalents per liter, therefore we first find the number of
equivalents
eq wt = FW/2 = 105.99/2 = 53.00
eq = Wt/eq wt = 5.300/53.00 = 0.1000
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N = eq/L = 0.1000 eq/1L = 0.1000 N

The problem can be worked out simply as below
? eq Na2CO3 /L = (5.300 g Na2CO3 /L ) x (1 mol Na2CO3 /105.99 g Na2CO3 ) x (2 eq
Na2CO3 /1 mol Na2CO3) = 0.1 N
The other choice is to find the molarity first and the convert it to normality using the relation
N=nM
No of mol = 5.300 g/(105.99 g/mol)
M = mol/L = [5.300 g/(105.99 g/mol)]/ 1L
N = n M = 2 x [5.300 g/(105.99 g/mol)]/ 1L = 0.1000
A further option is to find the number of moles first followed by multiplying the result by 2 to
obtain the number of equivalents.
Example
Find the normality of the solution containing 5.267 g/L K2Cr2O7 (FW = 294.19) if Cr6+ is
reduced to Cr3+.
Solution
The same as the previous example
N = eq/L , therefore we should find the number of eq where eq = wt/eq wt , therefore we
should find the equivalent weight where eq wt = FW/n. Here each Contributes three
electrons and since the dichromate contains two Cr atoms we have 6 reacting units
Eq wt = (294.19 g/mol)/(6 eq/mol)
Eq = 5.267 g/ (294.19 g/mol)/(6 eq/mol)
N = eq/L = (294.19 g/mol)/(6 eq/mol)/1L = 0.1074 eq/L
Using the dimensional analysis we may write
? eq K2Cr2O7 /L = (5.267 g K2Cr2O7 /L) x (mol K2Cr2O7 /294.19 g K2Cr2O7 ) x (6 eq
K2Cr2O7 /mol K2Cr2O7 ) = 0.0174 eq/L
Again one can choose to calculate the molarity then convert it to normality
mol = 5.267 g/(294.19 g/mol)
M = mol/L = [5.267 g/(294.19 g/mol)]/L
N=nM
N = (6 eq/mol)x [5.267 g/(294.19 g/mol)]/L = 0.1074 eq/L
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Density Calculations
In this section, you will learn how to find the molarity of solution from two pieces of
information ( density and percentage). Usually the calculation is simple and can be done using
several procedures. Look at the examples below:
Example
What volume of concentrated HCl (FW = 36.5g/mol, 32%, density = 1.1g/mL) are required to
prepare 500 mL of 2.0 M solution.
Solution
Always start with the density and find how many grams of solute in each mL of solution.
Remember that only a percentage of the solution is solute .
g HCl/ml = 1.1 x 0.32 g HCl / mL
The problem is now simple as it requires conversion of grams HCl to mmol since the molarity is
mmol per mL
mmol HCl = 1.1x0.32 x103 mg HCl/(36.5 mg/mmol) = 9.64 mmol
M = 9.64 mmol/mL = 9.64 M
Now, we can calculate the volume required from the relation
MiVi (before dilution) = MfVf (after dilution)
9.64 x VmL= 2.0 x 500mL
VmL = 104 mL
This means that 104 mL of the concentrated HCl should be added to distilled water and the
volume should then be adjusted to 500 mL
Example
How many mL of concentrated H2SO4 (FW = 98.1 g/mol, 94%, d = 1.831 g/mL) are required to
prepare 1 L of 0.100 M solution?
Solution
g H2SO4 / mL = 1.831 x 0.94 g /mL
Now find the mmol acid present
mmol H2SO4 = (1.831 x 0.94 x 1000 mg) / (98.1 mg/mmol)
The molarity can then be calculated as
M = mmol/mL = [(1.831 x 0.94 x 1000 mg) / (98.1 mg/mmol)] / mL = 17.5 M
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To find the volume required to prepare the solution

MiVi (before dilution) = MfVf (after dilution)
17.5 x VmL = 0.100 x 1000 mL
VmL = 5.71 mL which should be added to distilled water and then adjusted to 1 L.
Analytical Versus Equilibrium Concentration

When we prepare a solution by weighing a specific amount of solute and dissolve it in a specific
volume of solution, we get a solution with specific concentration. This concentration is referred
to as analytical concentration. However, the concentration in solution may be different
from the analytical concentration, especially when partially dissociating substances are
used. An example would be clear if we consider preparing 0.1 M acetic acid (weak acid) by
dissolving 0.1 mol of the acid in 1 L solution. Now, we have an analytical concentration of
acetic acid (HOAc) equals 0.1 M. But what is the actual equilibrium concentration of HOAc?
We have
HOAc = H+ + OAcThe analytical concentration ( CHOAc ) = 0.1 M
CHOAc = [HOAc]undissociated + [OAc-]
The equilibrium concentration = [HOAc]undissociated.
For good electrolytes which are 100% dissociated in water the analytical and equilibrium
concentrations can be calculated for the ions, rather than the whole species. For example, a 1.0
M CaCl2 in water results in 0 M CaCl2, 1.0 M Ca2+, and 2.0 M Cl- since all calcium
chloride dissociates in solution. For species x we express the analytical concentration as Cx
and the equilibrium concentration as [x]. All concentrations we use in calculations using
equilibrium constants are equilibrium concentrations.
Dilution Problems
In many cases, a dilution step or steps are involved in analytical procedures. One should always
remember that in any dilution the number of mmoles of the initial (concentrated) solution is
equal to the number of mmoles of the diluted solution. This means
MiVi (concentrated) = MfVf (dilute)
Example
Prepare 200 mL of 0.12 M KNO3 solution from 0.48 M solution.
Solution
0.48 x VmL = 0.12 x 200
VmL = (0.12 x 200)/0.48 = 50 mL
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Therefore, 50 mL of 0.48 M KNO3 should be diluted to 200 mL to obtain 0.12 M solution

Example
A 5.0 g Mn sample was dissolved in 100 mL water. If the percentage of Mn (At wt = 55 g/mol)
in the sample is about 5%. What volume is needed to prepare 100 mL of approximately 3.0x10-3
M solution.
Solution
First we find approximate mol Mn in the sample = 5.0 x (5/100) g Mn/(55 g/mol) = 4.5x10-3
mol
Molarity of Mn solution = (4.5x10-3 x 103 mmol)/100 mL = 4.5x10-2 M
The problem can now be solved easily using the dilution relation
4.5x10-2 x VmL = 3.0x10-3 x 100
VmL = (3.0x10-3 x 100)/4.5x10-2 = 6.7 mL
Therefore, about 6.7 mL of the Mn sample should be diluted to obtain an approximate
concentration of 3.0x10-3 M solution.
Expression of Analytical Results

A result can be reported as a percentage, part per thousand (ppt), part per million (ppm), part per
billion (ppb), etc.. Solutes can be solids , liquids, or gases. The concentration can be expressed
as weight solute per weight sample (w/w), weight solute per volume solution (w/v), or volume
solute per volume solution (v/v).
For Solid Solutes
% (w/w) = [weight solute (g)/weight sample (g)] x 100
ppt (w/w) = [weight solute (g)/weight sample (g)] x 1000
ppm (w/w) = [weight solute (g)/weight sample (g)] x 106
ppb (w/w) = [weight solute (g)/weight sample (g)] x 109
A ppm can be represented by several terms like the one above, (mg solute/kg sample), ( g
solute/106g sample), etc..
If the solute is dissolved in solution we have
% (w/v) = [weight solute (g)/volume sample (mL)] x 100
ppt (w/v) = [weight solute (g)/volume sample (mL)] x 1000
ppm (w/v) = [weight solute (g)/volume sample (mL)] x 106
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ppb (w/v) = [weight solute (g)/volume sample (mL)] x 109

Also a ppm can be expressed as above or as (g solute/106 mL solution), (mg solute/L
solution), or (g/mL),
etc..
(
For Liquid Solutes
% (v/v) = [volume solute (mL)/volume sample (mL)] x 100
ppt (v/v) = [volume solute (mL)/volume sample (mL)] x 1000
6
ppm (v/v) = [volume solute (mL)/volume sample (mL)] x 10
ppb (v/v) = [volume solute (mL)/volume sample (mL)] x 109

A ppm can be expressed as above or as (L/L),
(mL/103 L), etc..
(
It is very important here to recognize the similarity between the abovementioned relations
for easy remembrance of these terms when needed.
Example
A 2.6 g sample was analyzed and found to contain 3.6 g zinc. Find the concentration of zinc in
ppm and ppb.
Solution
A ppm is microgram solute per gram sample, therefore
Ppm Zn = 3.6 g Zn/2.6 g sample = 1.4 ppm
A ppb is nanogram solute/gram sample, therefore
Ppb Zn = 2.6 x103 ng Zn/2.6 g sample = 1400 ppb
Example
A 25.0 L sample was found to contain 26.7 g glucose. Express the concentration as ppm and
mg/dL glucose.
Solution
A ppm is defined as g/mL, therefore
Ppm = 26.7 g/(25.0x10-3 mL) = 1.07x103 ppm
Or one can use dimensional analysis considering always a ppm as mg/L as below
g) x (106 L/L) = 1.07x103 ppm
? mg/L glucose = (26.7 g/25.0 L) x (10-3 mg/
Now let us find mg glucose per deciliter
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?mg glucose/dL = = (26.7 g/25.0 L) x (10-3 mg/

g) x (106 L/L) x (L/10dL) = 107 mg/dL
The other important type of problems is to change from ppm or ppb into molarity and vice
versa
Example
Find the molar concentration of a 1.00 ppm Li (at wt = 6.94 g/mol) and Pb (at wt = 207 g/mol).
Solution
A 1.00 ppm is 1.00 mg/L, therefore change this 1.00 mg into moles to obtain molarity.
? mol Li/L = (1.00x10-3 g Li/L) x ( 1 mol Li/6.94 g Li) = 1.44x10-4 M
? mol Pb/L = (1.00x10-3 g Pb/L) x ( 1 mol Pb/207 g Li) = 4.83x10-6 M
Example
Find the number of mg Na2CO3 (FW = 106 g/mol) required to prepare 500 mL of 9.20 ppm Na
solution.
Solution
The idea is to find the of mg sodium ( 23.0 mg/mmol) required and then get the mmoles
sodium and relate it to mmoles sodium carbonate followed by calculation of the weight of
sodium carbonate.
? mg Na = 9.20 mg/L x 0.5 L = 4.6 mg Na
mmol Na = 4.60 mg Na/23.0 mg/mmol
mmol Na2CO3 = 1/2 mmol Na = 4.60/46.0 mmol = 0.100
? mg Na2CO3 = (4.60/46.0) mmol Na2CO3 x (106 mg Na2CO3/ mmol Na2CO3) = 10.6 mg
One can work such a problem in one step as below
? mg Na2CO3 = (9.2 mg Na/1000mL) x 500 mL x (1mmol Na/23.0 mg Na) x (1 mmol
Na2CO3/2 mmol Na) x (106 mg Na2CO3/1 mmol Na2CO3) = 10.6 mg
Stoichiometric Calculations: Volumetric Analysis

In this section we look at calculations involved in titration processes as well as general
quantitative reactions. In a volumetric titration, an analyte of unknown concentration is titrated
with a standard in presence of a suitable indicator. For a reaction to be used in titration the
following characteristics should be satisfied:
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1. The stoichiometry of the reaction should be exactly known. This means that we should
know the number of moles of A reacting with 1 mole of B.
2. The reaction should be rapid and reaction between A and B should occur immediately and
instantly after addition of each drop of titrant (the solution in the burette).
3. There should be no side reactions. A reacts with B only.
4. The reaction should be quantitative. A reacts completely with B.
5. There should exist a suitable indicator which has distinct color change.
6. There should be very good agreement between the equivalence point (theoretical) and the
end point (experimental). This means that Both points should occur at the same volume of
titrant or at most a very close volume. Three reasons exist for the disagreement between the
equivalence and end points. The first is whether the suitable indicator was selected, the
second is related to concentration of reactants, and the third is related to the value of the
equilibrium constant. These factors will be discussed in details later in the course.
Standard solutions
A standard solution is a solution of known and exactly defined concentration. Usually standards
are classified as either primary standards or secondary standards. There are not too many
secondary standards available to analysts and standardization of other substances is necessary to
prepare secondary standards. A primary standard should have the following properties:
1. Should have a purity of at least 99.98%
2. Stable to drying, a necessary step to expel adsorbed water molecules before weighing
3. Should have high formula weight as the uncertainty in weight is decreased when weight is
increased
4. Should be non hygroscopic
5. Should possess the same properties as that required for a titration
NaOH and HCl are not primary standards and therefore should be standardized using a
primary or secondary standard. NaOH absorbs CO2 from air, highly hygroscopic, and usually of
low purity. HCl and other acid in solution are not standards as the percentage written on the
reagent bottle is a claimed value and should not be taken as guaranteed.
Molarity Volumetric Calculations
Volumetric calculations involving molarity are rather simple. The way this information is
presented in the text is not very helpful. Therefore, disregard and forget about all equations and
relations listed in rectangles in the text, you will not need it. What you really need is to use the
stoichiometry of the reaction to find how many mmol of A as compared to the number of mmoles
of B.
Example
A 0.4671 g sample containing NaHCO3 (FW = 84.01 mg/mmol) was dissolved and titrated with
0.1067 M HCl requiring 40.72 mL. Find the percentage of bicarbonate in the sample.
Solution
We should write the equation in order to identify the stoichiometry
NaHCO3 + HCl = NaCl + H2CO3
Now it is clear that the number of mmol of bicarbonate is equal to the number of mmol HCl
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Mmol NaHCO3 = mmol HCl

Mmol = M x VmL
Mmol NaHCO3 = ( 0.1067 mmol/ml ) x 40.72 mL = 4.345 mmol
Now get mg bicarbonate by multiplying mmol times FW
Mg NaHCO3 = 4.345 mmol x (84.01 mg/mmol) = 365.01
% NaHCO3 = (365.01 x 10-3 g/0.4671 g) x 100 = 78.14%
We can use dimensional analysis to calculate the mg NaHCO3 directly then get the percentage as
above.
? mg NaHCO3 = (0.1067 mmol HCl/ml) x 40.72 mL x (mmol NaHCO3/mmol HCl) x (84.01 mg
NaHCO3/ mmol NaHCO3) = 365.0 mg
Example
A 0.4671 g sample containing Na2CO3 (FW = 106mg/mmol) was dissolved and titrated with
0.1067 M HCl requiring 40.72 mL. Find the percentage of carbonate in the sample.
Solution
The equation should be the first thing to formulate
Na2CO3 +2 HCl = 2NaCl + H2CO3
Mmol Na2CO3 = mmol HCl
Now get the number of mmol Na2CO3 = x ( MHCl x VmL (HCl) )
Now get the number of mmol Na2CO3 = x 0.1067 x 40.72 = 2.172 mmol
Now get mg Na2CO3 = mmol x FW = 2.172 x 106 = 230 mg
% Na2CO3 = (230 x 10-3 g/0.4671 g ) x 100 = 49.3 %
Example
How many mL of 0.25 M NaOH will react with 5.0 mL of 0.10 M H2SO4.
H2SO4 + 2 NaOH = Na2SO4 + 2 H2O
Solution
Mmol NaOH = 2 mmol H2SO4
Mmol NaOH = 2 {M (H2SO4) x VmL (H2SO4)}
Mmol NaOH = 2 x 0.10 x 5.0 = 1.0 mmol
Mmol NaOH = MNaOH x VmL (NaOH)
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1.0 = 0.25 x VmL

VmL = 4.0 mL
We can also calculate the volume in one step using dimensional analysis
? mL NaOH = (mL NaOH/0.25 mmol NaOH) x (2 mmolNaOH/mmol H2SO4) x (0.10 mmol
H2SO4 / mL H2SO4) x 5.0 mL = 4.0 mL
In a previous lecture you were introduced to calculations involved in titrimetric reactions. We
agreed that you do not have to memorize relations listed in the text and the only relation you need
to remember is the mmol. A mmol is mg/FW or molarity times volume (mL). We have also
agreed that writing the equation of the reaction is essential and is the first step in solving any
problem where a reaction takes place. Let us look at more problems and develop a logic solution
using the simple mmol concept.
Example
A 0.1876 g of sodium carbonate (FW = 106 mg/mmol) was titrated with approximately 0.1 M HCl
requiring 35.86 mL. Find the molarity of HCl.
Solution
The first thing to do is to write the equation. For the reaction. You should remember that
carbonate reacts with two protons
Na2CO3 + 2 HCl = 2 NaCl + H2CO3
The second step is to relate the number of mmol HCl to mmol carbonate, Where it is clear from
the equation that we have 2 mmol HCl and 1 mmol carbonate. This is translated to the following
Mmol HCl = 2 mmol Na2CO3
Now let us substitute for mmol HCl by MHCl X VmL, and substitute for mmol carbonate by mg
carbonate/FW carbonate. This gives
MHCl x 35.86 = 187.6 mg/ (106 mg/mmol)
MHCl = 0.09872 M
The same result can be obtained using dimensional analysis in one single step:
? mmol HCl/mL = (187.6 mg Na2CO3 /35.86 mL HCl) x ( mmol Na2CO3/106 mg Na2CO3) x (2
mmol HCl/mmol Na2CO3) = 0.09872 M
Example
An acidified and reduced iron sample required 40.2 mL of 0.0206 M KMnO4. Find mg Fe (at wt =
55.8) and mg Fe2O3 (FW = 159.7 mg/mmol).
Solution
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The first step is to write the chemical equation

MnO4- + 5 Fe2+ + 8 H+ = Mn2+ + 5 Fe3+ + 4 H2O
MnO4- + 2.5 Fe22+ + 8 H+ = Mn2+ + 5 Fe3+ + 4 H2O
Mmol Fe = 5 mmol KMnO4
Now substitute for mf Fe by mg Fe/at wt Fe and substitute for mmol KMnO4 my molarity of
permanganate times volume, we then get
[mg Fe/(55.8 mg/mmol)] = 5 x (0.0206 mmol/mL) x 40.2 mL
mg Fe = 231 mg
This can also be done in a single step as follows:
? mg Fe = (0.0206 mmol KMnO4 /mL) x 40.2 mL x (5 mmol Fe/mmol KMnO4) x ( 55.8 mg
Fe/mmol Fe) = 231 mg
To calculate the mg Fe2O3 we set the following
Mmol Fe2O3 = 2.5 mmol KMnO4
[mg Fe2O3/ (159.7 mg/mmol)] = 2.5 x (0.0206 mmol/mL) x 40.2 mL
mg Fe2O3 = 331 mg
The last step can also be done using dimensional analysis as follows:
? mg Fe2O3 = = (0.0206 mmol KMnO4 /mL) x 40.2 mL x (5 mmol Fe2O3 /mmol KMnO4) x
( 55.8 mg Fe2O3/mmol Fe) = 331 mg
Example
A 1.00 g Al sample required 20.5 mL EDTA. Find the % Al2O3 (FW = 101.96) in the sample if
30.0 mL EDTA required 25.0 mL of 0.100 M CaCl2.
Solution
We should know that EDTA reacts in a 1:1 ratio with metal ions Therefore, the equation is
Al + EDTA = Al-EDTA
AL2O3 + 2 EDTA = 2 Al-EDTA
Therefore, 1 mmol Al2O3 reacts with 2 mmoles EDTA since it contains 2 mmol AL
Mmol Al2O3 = mmol EDTA
(1)
The same procedure above is repeated in the calculation. First we substitute mg aluminum
oxide/FW for the mmol of aluminum oxide and substitute mmol EDTA by molarity times volume.
But we do not have the molarity of EDTA, therefore,let us calculate the molarity of EDTA.
Mmol EDTA = mmol Ca
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Molarity x VmL(EDTA) = Molarity x VmL (Ca)

MEDTA x 30.0 = 0.100 x 25.0
MEDTA = 0.0833 M
Now we can solve the problem using relation (1)
[mg Al2O3/ ( 101.96 mg/mmol)] = x 0.833 x 20.5
? mg Al2O3 = 87.1 mg
% Al2O3 = (87.1 mg/1000 mg) x 100 = 8.71%
After calculation of the molarity of EDTA, one can do the rest of the calculation in a single step as
follows:
? mg Al2O3 = (0.0833 mmol EDTA/mL) x 20.5 mL x (mmol Al2O3/2mmol EDTA) x (101.96
mg Al2O3/mmol Al2O3) = 87.1 mg
Back to Dilution Problems

We have indicated earlier that the key to solve any dilution problem is to remember that the
number of mmol is the same in both initial and final solutions. Dilution decreases the
concentration but the volume increases where the mmol remains constant.
Example
What volume of 0.4 M Ba(OH)2 should be added to 50 mL of 0.30 M NaOH in order to obtain a
solution that is 0.5 M in OH-.
Solution
We have to be able to see that the mmol OH- coming from Ba(OH)2 and NaOH will equal the
number of mmol of OH- in the final solution, which is
Mmol OH- from Ba(OH)2 + mmol OH- from NaOH = mmo OH- in final solution
The mmol OH- from Ba(OH)2 is molarity of OH- times volume and so are other terms.
Molarity of OH- from Ba(OH)2 is 0.8 M (twice the concentration of Ba(OH)2, and its volume
is x mL. Now performing the substitution we get
0.8 x x + 0.30 x 50 = 0.5 x (x + 50)
x = 33 mL
We have seen in previous sections that correct solution of any problem involving reactions
between two substances requires setting up two important relations:
2/3/2015
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1.
Writing a balanced chemical equation representing stoichiometric

relationships.
2. Formulating a relationship between the number of mmol of substance A and
mmol of substance B.
The last step in the calculation is to substitute for the mmol A or B by either one of the following
according to given information:
1. mmol = M x VmL
2. mmol = mg/FW
Only one unknown will be encountered and should be easily determined following the
abovementioned steps.
Example
Find the volume of 0.100 M KMnO4 that will react with 50.0 mL of 0.200 M H2O2 according to
the following equation:
5 H2O2 + 2 KMnO4 + 6 H+ = 2 Mn2+ + 5 O2 + 8 H2O
Solution
We have the equation ready therefore the following step is to formulate the relationship between
the number of moles of the two reactants. We always start with the one we want to calculate, that
is
mmol KMnO4 = 2/5 mmol H2O2
It is clear that we should substitute M x VmL for mmol in both substances as this information is
given to us.
0.100 x VmL = 2/5 x 0.200 x 50.0
VmL = 40.0 mL KMnO4
Example
Find the volume of 0.100 M KMnO4 that will react with 50.0 mL of 0.200 M MnSO4 according to
the following equation:
3 MnSO4 + 2 KMnO4 + 4 OH- = 2 MnO2 + 2 H2O + 2 K+ + SO42Solution
Again, we have the equation ready therefore we turn to formulating a relationship for the number
of mmol for both substances.
mmol KMnO4 = 2/3 mmol MnSO4
It is clear that we should substitute M x VmL for mmol in both substances as this information is
given to us.
2/3/2015
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0.100 x VmL = 2/3 x 0.200 x 50.0

VmL = 66.7 mL KMnO4
Example
Find the volume of 0.100 M KMnO4 that will react with 500 mg of H2C2O4 (FW = 90.0mg/mmol)
according to the following equation:
5 H2C2O4 + 2 KMnO4 + 6 H+ = 10 CO2 + 2 Mn2++ 8 H2O + 2 K+
Solution
We have the equation ready therefore we turn to formulating a relationship for the number of
mmol for both substances.
mmol KMnO4 = 2/5 mmol H2C2O4
It is clear that we should substitute M x VmL for mmol permanganate while substitute for mmol
oxalic acid by mg/FW. This gives:
0.100 x VmL = 2/5 x 500 mg / (90.0 mg/mmol)
VmL = 22.2 mL KMnO4
Back-Titrations
In this technique, an accurately known amount of a reagent is added to analyte in such a way that
some excess of the added reagent is left. This excess is then titrated to determine its amount and
thus:
mmol reagent taken = mmol reagent reacted with analyte + mmol reagent titrated
Therefore, the analyte can be determined since we know mmol reagent added and mmol reagent
titrated.
mmol reagent reacted = mmol reagent taken mmol reagent titrated
Finally, the number of mmol reagent reacted can be related to the number of mmol analyte from
the stoichiometry of the reaction between the two substances.
Why Do We Use Back-Titrations?
Back-titrations are important especially in some situations like:
1. When the titration reaction is slow. Addition of an excess reagent will force the
reaction to proceed faster.
2. When the titration reaction lacks a good indicator. We will see details of this later.
3. When the analyte is not very stable. Addition of excess reagent will finish the
analyte instantly thus overcoming stability problems.
Example
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A 2.63 g Cr(III) sample was dissolved and analyzed by addition of 5.00 mL of 0.0103 M EDTA.
The excess EDTA required 1.32 mL of 0.0112 M Zn(II). Calculate % CrCl3 (FW=158.4
mg/mmol) in the sample.
Solution
We should remember that EDTA reacts in a 1:1 ratio. The first step in the calculation is to find the
mmol EDTA reacted from the relation:
mmol EDTA reacted = mmol EDTA taken mmol EDTA titrated
We substitute for both mmol EDTA taken and mmol EDTA titrated by M x VmL for each. Also
since EDTA reacts in a 1:1 ratio, we can state the following:
1. mmol EDTA reacted = mmol CrCl3.
2. mmol EDTA titrated = mmol Zn(II).
Therefore, we now have the following reformulated relation:
mmol CrCl3 = mmol EDTA taken mmol Zn(II)
Substitution gives:
mmol CrCl3 = 0.0103 x 5.00 0.0112 x 1.32
mmol CrCl3 = 0.0367 mmol
We can then find the number of mg CrCl3 by multiplying mmol times FW.
Mg CrCl3 = 0.0367 mmol x 158.4 mg/mmol = 5.81 mg
% CrCl3 = (5.81 mg/2.63x103 mg) x 100 = 0.221%
Example
A 0.500 g sample containing sodium carbonate (FW=106 mg/mmol) was dissolved and analyzed
by addition of 50.0 mL of 0.100 M HCl solution. The excess HCl required 5.6 mL of 0.05 M
NaOH solution. Find the percentage of Na2CO3 n the sample.
Solution
First, write the chemical equations involved
Na2CO3 + 2 HCl = 2 NaCl + H2CO3
HCl + NaOH = NaCl + H2O
mmol HCl reacted = mmol HCl taken mmol HCl titrated
1. mmol HCl reacted = 2 mmol Na2CO3
2. mmol HCl titrated = mmol NaOH
Now we can reformulate the above relation to read
2/3/2015
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2 mmol Na2CO3 = mmol HCl taken mmol NaOH

mmol Na2CO3 = 1/2 ( 0.100 x 50.0 0.050 x 5.6) = 2.36 mmol
? mg Na2CO3 = 2.36 mmol x 106 mg/mmol = 250 mg
% Na2CO3 = (250 mg/0.500 x103 mg) x 100 = 50.0%
Example
A 0.200 g sample containing MnO2 was dissolved and analyzed by addition of 50.0 mL of 0.100
M Fe2+ to drive the reaction
2 Fe2+ + MnO2 + 4 H+ = 2 Fe3+ + Mn2+ + 2 H2O
The excess Fe2+ required 15.0 mL of 0.0200 M KMnO4. Find % Mn3O4 (FW= 228.8 mg/mmol) in
the sample.
5 Fe2+ + MnO4- + 8 H+ = 5 Fe3+ + Mn2+ + 4 H2O
Solution
First, calculate mmol MnO2 then change it to mmol Mn3O4 . We have the relation
mmol Fe2+ reacted = mmol Fe+ taken mmol Fe+ titrated
Now we should perform the following substitutions:
1. mmol Fe2+ reacted = 2 mmol MnO2
2. mmol Fe2+ titrated = 5 mmol KMnO4
Now reformulate the above relation:
2 mmol MnO2 = mmol Fe2+ taken 5 mmol KMnO4
Substitution gives:
mmol MnO2 = 1/2( 0.100 x 50.0 5 x 0.0200 x 15.0) = 1.75 mmol
3 MnO2 = Mn3O4 + O2
mmol Mn3O4 = 1/3 mmol MnO2
mmol Mn3O4 = 1/3 x 1.75 mmol = 0.5833
?mg Mn3O4 = 0.5833 mmol x 228.8 mg/mmol = 133.5 mg
% Mn3O4 = (133.5 mg/200 mg) x 100 = 66.7%
Normality volumetric Calculations

We have seen previously that solving volumetric problems required setting up a relation between
the number of mmoles or reacting species. In case of normality, calculation is easier as we always
have the number of milli equivalents (meq) of substance A is equal to meq of substance B,
2/3/2015
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regardless of the stoichiometry in the chemical equation. Of course this is because the number of
moles involved in the reaction is accounted for in the calculation of meqs.
Therefore, the first step in a calculation using normalities is to write down the relation
meq A = meq B
The next step is to substitute for meq by one of the following relations
1. meq = N x VmL
2. meq = mg/eq wt
3. meq = n x mmol
We should remember from previous lectures that:
1. eq wt = FW/n
2. N = n x M
Therefore, change from molarity or number of moles to normality or number of equivalents
using the above relations.
Again, I believe you do not have to remember the long relations presented in the text and keep
things simple by following the steps I suggest for you to solve any normality volumetric problem.
The most direct way for understanding these concepts is to look at the following examples:
Example
A 0.4671 g sample containing sodium bicarbonate was titrated with HCl requiring 40.72 mL. The
acid was standardized by titrating 0.1876 g of sodium carbonate (FW = 106 mg/mmol) requiring
37.86 mL of the acid. Find the percentage of NaHCO3 (FW=84.0 mg/mmol) in the sample.
Solution
This problem was solved previously using molarity. The point here is to use normalities in order
to practice and learn how to use the meq concept. First, let us find the normality of the acid from
reaction with carbonate (reacts with two protons as you know).
Eq wt Na2CO3 = FW/2 = 53 and eq wt NaHCO3 = FW/1 = 84.0
meq HCl = meq Na2CO3
Now substitute for meq as mentioned above:
Normality x volume (mL) = wt (mg)/ eq wt
N x 37.86 = 0.4671 x 1000 mg/ (53 mg/meq)
NHCl= 0.0935 eq/L
Now we can find meq NaHCO3 where
meq NaHCO3 = meq HCl
mg NaHCO3 / eq wt = N x VmL
mg NaHCO3 /84.0 = 0.0935 x 40.72
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mg NaHCO3 = 84.0 x 0.0935 x 40.72 mg

% NaHCO3 = (84.0 x 0.0935 x 40.72 mg/476.1 mg) x 100 = 67.2%
Example
Use normalities to calculate how many mL of a 0.10 M H2SO4 will react with 20 mL of 0.25 M
NaOH.
Solution
We can first convert molarities to normalities:
N=nxM
N (H2SO4) = 2 x 0.10 = 0.20
N (NaOH) = 1 x 0.25 = 0.25
meq H2SO4 = meq NaOH
Substitute for meq as usual ( either NVmL or mg/eq wt)
0.20 x VmL = 0.25 x 20
VmL = 25 mL
Example
Find the normality of sodium carbonate (FW = 106) in a solution containing 0.212 g carbonate in
100 mL solution if :
a. The carbonate is used as a monobasic base.
b. The carbonate is used as a dibasic base.
Solution
If carbonate is a monobasic base then eq wt = FW/1 = 106/1 = 106 mg/meq
To find the normality of the solution we find the weight per mL and then convert the weight per
mL to meq/mL. We have 212 mg/100 mL which means 2.12 mg/mL. Now the point is how many
meq per 2.12 mg sodium carbonate.
meq = mg/eq wt = 2.12/106 = 0.02 meq
Then the normality is 0.02 N
If carbonate is to be used as a dibasic salt then the eq wt = FW/2 = 106/2 = 53 mg/meq.
To find the normality of the solution we find the weight per mL and then convert the weight per
mL to meq/mL. We have 212 mg/100 mL which means 2.12 mg/mL. Now the point is how many
meq per 2.12 mg sodium carbonate.
meq = mg/eq wt = 2.12/53 = 0.04 meq
Then normality will be 0.04 N
Example
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How many mg of I2 (FW = 254 mg/mmol) should you weigh to prepare 250 mL of 0.100 N
solution in the reaction:
I2 + 2e = 2 ISolution
To find the number of mg I2 to be weighed and dissolved we get the meq required. We have:
meq = N x VmL
meq = 0.100 x 250 = 25.0 meq
mg I2 = meq x eq wt = meq x FW/2 = 25.0 x 254/2 = 3.18x103 mg
Example
Find the normality of the solution containing 0.25 g/L H2C2O4 (FW = 90.0 mg/mmol). Oxalic acid
reacts as a diacidic substance.
Solution
Since oxalic acid acts as a diacidic substance then its eq wt = FW/2 = 90.0/2 = 45.0 mg/meq
We convert the mg acid per mL to meq acid per mL We have 0.25 mg acid/mL
meq acid = 0.25 mg/45.0 mg/meq = 0.0056 meq
Therefore, the normality is 0.0056 meq/mL
The Titer Concept

In many situations where routine titrations are carried out and to avoid wasting time in performing
calculations, one can calculate the weight of analyte in mg equivalent to 1 mL of titrant. The
obtained value is called the titer of the titrant. For example, an EDTA bottle is labeled as having a
titer of 2.345 mg CaCO3. This means that each mL of EDTA consumed in a titration of calcium
carbonate corresponds to 2.345 mg CaCO3. If the titration required 6.75 mL EDTA then we have
in solution 2.345 x 6.75 mg of calcium carbonate.
Example
What is the titer of a 5.442g/L K2Cr2O7 (FW = 294.2 mg/mmol) in terms of Fe2O3 (FW = 159.7
mg/mmol). The equation is:
6 Fe2+ + Cr2O72- + 14 H+ = 6 Fe3+ + 2 Cr3+ + 7 H2O
Solution
1 mL of K2Cr2O7 contains 5.442 mg K2Cr2O7 per mL. Therefore let us find how many mg Fe2O3
corresponds to this value of K2Cr2O7.
mmol K2Cr2O7 per mL = 5.442 mg/294.2 mg/mmol = 0.0185
mmol Fe2O3 = 3 mmol K2Cr2O7
mmol Fe2O3 = 3 x 0.0185 = 0.0555 mmol
mg = mmol x FW
2/3/2015
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mg Fe2O3 = 0.0555 mmol x (159.7 mg/mmol) = 8.86 mg

Therefore, the titer of K2Cr2O7 in terms of Fe2O3 is 8.86 mg Fe2O3 per mL K2Cr2O7
2/3/2015

Stoichiometric Calculations: Review of Fundamental Concepts

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Stoichiometric Calculations

Review of Fundamental Concepts

Calculations involving solutions

Calculations Involving Molarity

mmol Na2SO4 = 0.1 mmol/mL x 500 mL = 50 mmol

Or, number of milliequivalents = wt(mg)/equivalent weight (mg/meq)

N = eq/L = 0.1000 eq/1L = 0.1000 N

To find the volume required to prepare the solution

Analytical Versus Equilibrium Concentration

Therefore, 50 mL of 0.48 M KNO3 should be diluted to 200 mL to obtain 0.12 M solution

Expression of Analytical Results

ppb (w/v) = [weight solute (g)/volume sample (mL)] x 109

ppm (v/v) = [volume solute (mL)/volume sample (mL)] x 10

ppb (v/v) = [volume solute (mL)/volume sample (mL)] x 109

?mg glucose/dL = = (26.7 g/25.0 L) x (10-3 mg/

Stoichiometric Calculations: Volumetric Analysis

Mmol NaHCO3 = mmol HCl

1.0 = 0.25 x VmL

The first step is to write the chemical equation

Molarity x VmL(EDTA) = Molarity x VmL (Ca)

Back to Dilution Problems

Writing a balanced chemical equation representing stoichiometric

0.100 x VmL = 2/3 x 0.200 x 50.0

2 mmol Na2CO3 = mmol HCl taken mmol NaOH

Normality volumetric Calculations

mg NaHCO3 = 84.0 x 0.0935 x 40.72 mg

The Titer Concept

mg Fe2O3 = 0.0555 mmol x (159.7 mg/mmol) = 8.86 mg

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