STOICHIOMETRY - BASIS OF CHEMICAL CALCULATIONS

Chemistry is an experimental science. It’s the study of chemical reactions and composition of
substances, qualitative and quantitative. The last is very important, because chemistry is a
quantitative science. Formulas and equations provide lots of valuable information about the
composition of substances and their relationship. This part of chemistry associated to a
quantitative relationship between amounts of materials is called stoichiometry. Stoichiometry
(derived from the Greek words, stoicheion = element and metron = measure) is the term we use in
describing the quantitative aspects of chemical composition and reaction.

CHEMICAL CALCULATIONS

CALCULATIONS BASED ON CALCULATIONS BASED ON

CHEMICAL FORMULAS CHEMICAL REACTIONS
(COMPOUND STOICHIOMETRY) (REACTION STOICHIOMETRY)

Finding the composition of Finding the formula of a The reactants The reactants
a compound (i.e. % of the compound; empirical and are in a are not in a
elements) whose formula molecular, knowing the stoichiometric stoichiometric
is known. percent composition of ratio. ratio
Пресметување на the compound. Реактантите се Реактантите не
составот на Наоѓање на формулата во стехиомет- се во стехио-
соединението т.е. на соединение риски однос метриски однос
определување на (емпириска и/или
содржината на молекулска) од познат
елементите (молски и состав т.е. содржина на
масени удели; %) во елементите (уделите)
дадено соединение

PART I. Calculations based on chemical formulas

To express the quantitative composition of a compound, two types of calculations can be done:
 Determining the molar or mass ratios of the elements in a compound (formula is known)
 Determining the abundance (usually in %) of the chemical elements in a compound, better
known as fractions. In a fact, abundance can be measured in one of the three ways: by the mass-
fraction, by the mole-fraction or by the volume-fraction.
 Determining mole and mass ratios of elements in compounds
Practice examples. The compound iron(III) sulphide has a formulae Fe2S3.
Fe2S3 is an empirical formula showing the ratio of the two types of ions; Fe3+ and S2 (ionic
compound) hence the ionic ratio is 2 : 3. The subscripts 2 and 3 in the formula of this compound
also indicates the number of moles of each element, meaning that in a mole of Fe2S3 there are
two moles of iron and three moles of sulphur or their ratio mathematically can be expressed as:
n(Fe) : n(S) = 2 : 3
Subscripts can be taken to calculate mass ratio between elements which in this case is: 112 : 96.
REMEMBER that the mass of an element in a compound can be computed as a product between
the subscript and the relative atomic mass of the element i.e. m(E) = i(E) ∙ Ar(E)
The mass ratio of the elements in Fe2S3 can be then calculated as:
m(Fe) : m(S) = 2Ar(Fe) : 3Ar(S) = 256 : 332 = 112 : 96

1. Calculate the mole and mass ratio of the elements in the given compounds.
HOMEWORK
a) Na2SO4 b) Ca3(PO4)2 c) MgSO4  7H2O

2. Calculate mole and mass fractions (in %) of all the elements in the above compounds.

 Determining percent composition i.e. mole and mass fraction of elements in

compounds:
Example: If a class of 34 students in total has 16 boys and 18 girls, the % of the girls is given to be:
number of the girls  100 % 18  100 %
% of the girls = = = 52,94 %
total number of the students 34

hence the % of the boys = (100 – 52,94)% = 47,06 % NOTE: Even though mass has units,
mass percent is unit-less, and so
x(E, X) = n(E)/n  100% care needs to be taken to identify
what the percent or fraction relates
mole fraction (%) amount of the element E to. Because a sample of a pure
substance consists of molecules or
количествен (молски) удел
ions (if the compound is ionic), the
total amount of all elements in the compound X i.e. n percent i.e. fractional value does
(Greek uppercase letter sigma indicates sum (збир) not depend on the sample size.
Which means that one molecule of
Example 1. Calculate the mole percents of Fe and Cl in FeCl3. water has the same percent
FeCl3 n(Fe) = 1 mol composition as a gallon of water
(pure or distillated water).
n(Cl) = 3 mol
n = n(Fe) + n(Cl) = 1 mol + 3 mol = 4 mol
x(Fe, FeCl3) = n(Fe)/n 100% = 1 mol/4 mol  100% = 25 % no unit!
x(Cl, FeCl3) = 100 % - 25 % = 75 %

w(E, X) = m(E)/m  100% = i(E)  Ar(E)/Mr(X)  100%

mass fraction (%)

mass (%) fraction of a given mass (%) fraction of a given element in a compound X
substance in solutions (if the chemical formula of the compound is known)

Example 2. Calculate percents of iron and chlorine by mass in the compound FeCl3. Ar(Fe) = 56
FeCl3 Ar(Cl) = 35,4
knowing that: m(E) = i(E)  Ar(E)  m(Fe) = i(Fe)  Ar(Fe)
m = Mr(FeCl3) = Ar(Fe) + 3Ar(Cl) = 56 + 335,4 = 162,2
hence w(Fe, FeCl3) = i(Fe)  Ar(Fe) / Mr(FeCl3) 100% = 156 / 162,2 100% = 34,52 %
w(Cl, FeCl3) = i(Cl)  3Ar(Fe) / Mr(FeCl3) 100% = 335,4 / 162,2 100 % = 65,48 %
or the mass % of Cl can be calculated by subtraction of the iron’s percent from 100 %
w(Cl, FeCl3) = 100 % - 34,52 % = 65,48 %

 Determining empirical and molecular formula of a compound from its percent

composition
I начин
A binary compound can be presented by the formula AxBy, whereas x and y are the subscripts of
the elements A and B respectively. In this type of calculations we know the elements of which the
compound is made from but the subscripts of the elements have to be determined.
We know that the mass fraction of an element A in a compound AxBy will be given by the ratio:
w(A) = i(A)Ar(A) / Mr(AxBy)  the subscript, i(A) then will be given by the following ratio:
i(A) = w(A) Mr(AxBy) /Ar(A)
Assume we have a compound AxBy  x = i(A) and y = i(B) therefore the equation to find an
empirical and molecular formula can be presented as following:
w(A) w(B)
i(A) : i(B) =  Mr(AxBy) :  Mr(AxBy)  equation used to find molecular
Ar(A) Ar(B)
formula

w(A) w(B)  equation used to find empirical formula (notice

i(A) : i(B) = : Mr(AxBy) in the above ratio are cancel each other out
Ar(A) Ar(B)
hence the ratio of the subscripts can be simplified as is
given in the equation on the left)

II начин
If mass percents of the elements A and B are given then we can assume that in 100 grams of a
sample of this compound we had the same number of grams of A and B respectively.
For example if the mass percent of the element A is 35 %, in 100 g sample of this compound would be 35 g
of the element A (and 65 g of the element B).
m(A) = 35 g m(B) = 100 g  35 g = 65 g (same as finding the mass % of B; 100% - 45%)
Here from dividing masses of the elements by their molar masses we can calculate the amounts of
A and B respectively.
n(A) = m(A)/M(A) n(B) = m(B)/M(B) (molar masses are always equal to the Ar(E) expressed in
grams per mole.)
Finally, from their amount’s ratio you can determine subscripts A and B in the compound that is its
empirical formula.

Practice example
1. Copper forms two compounds with chlorine. One of them consists of 47.22% copper and the
rest is chlorine by mass. What’s the empirical formula of this compound?
I начин The assumed empirical formula is: CuxCly Given data: w(Cu) = 47,22 % = 0,4722
w(Cu) w(Cl) w(Cl) = 52,78 % = 0,5278
i(Cu) : i(Cl) = :
Ar(Cu Ar(Cl
) )
 0,4722 0,5278 Remember: Do not work with mass %
i(Cu) : i(Cl) = : in this type of calculations. Convert
63,5 35,4 mass % to a decimal number by
dividing it by 100%.

i(Cu) : i(Cl) = 0,0074 : 0,0149 / 0,0074 (и двата броја се делат со најмалиот од нив!)
i(Cu) : i(Cl) = 1 : 2,01 = 1 : 2 hence the empirical formula is CuCl2

II начин
This means that if we had a 100 g sample of this substance, it would contain 47,22 g of copper (Cu)
and 52,78 g of chlorine (Cl). (Notice: any size sample can be used in problems of this type, but we
will generally use 100 g to make the calculation of mass from percentage easy).
Given data: m(Cu) = 47,22 g m(Cl) = 52,78 g Ar(Cu) = 63,5 Ar(Cl) = 35,4
From the above data the empirical formula can be found throughout following steps:
STEP 1
The assumed empirical formula of a compound formed by the two elements, copper and chlorine
is CuxCly, wheres "x" and "y" are the subscripts of the two elements. Subscripts also represent the
number of moles of each element therefore the subscript x = n(Cu) whereas y = n(Cl)
STEP 2
To calculate the number of moles of each element in 100 g, divide the mass of each element by its
molar mass (recall that the relationship between m and n was given by the equation: m = n ∙ M):
x = n(Cu) = m(Cu)/M(Cu) = 47,22 g/63,5 g/mol = 0,7436 mol
y = n(Cl) = m(Cl)/M(Cl) = 52,78 g/35,5 g/mol = 1,4867 mol
STEP 3
As you now subscripts are whole-numbers, hence to get subscripts as whole-numbers divide the
number of moles of each element by the smallest number of moles which in this case is 0,7436;
x : y = n(Cu) : n(Cl) = 0,7436 mol / 0,7436 mol : 1,4867 mol / 0,7436
x : y = 1 : 1,999 i.e. 1 : 2
The subscripts are 1 and 2, here from the empirical formula for a compound composed of copper
and chlorine is CuCl2. This is empirical formula because subscripts show the smallest whole-
number ratio of ions in a formula unit (or in the compound).

Similar to above calculations, if two or more substances form a mixture then the mole and mass
fractions can be calculated in the same way as the calculations done from a given chemical
formula. Hence the mass % can be found using the formula: w(A) = m(A)/msol.  100 % whereas
the letter A symbolizes the component A that is dissolved in the solvent making the solution.

Example.: Calculate the mole and mass percents of table salt (NaCl) in 250 g water solution if 3 g
of sodium chloride are dissolved in water.
Given data: m(NaCl) = 3 g
msol = 250 g (msol is the total mass of the solution obtained by addition of the
mass of water and mass of NaCl)
SOLUTION: w(A) = m(A)/msol. 100 %
w(NaCl, solution) = m(NaCl, sol.)/msol. 100 % = 3 g/250 g  100 % = 1,2 %

x(A) = n(A)/nsol. 100 % i.e. x(NaCl) = n(NaCl)/nsol. 100 %

hence n(NaCl) = m(NaCl)/M(NaCl) = 3 g/58,4 g∙mol-1 = 0,051 mol
nsol. = n(NaCl) + n(H2O)
msol. = m(NaCl) + m(H2O)  m(H2O) = msol  m(NaCl) = 250 g  3 g = 247 g
n(H2O) = m(H2O)/M(H2O) = 247 g/18 g∙mol-1 = 13,72 mol
nsol. = n(NaCl) + n(H2O) = 0,051 mol + 13,72 mol = 13,77 mol
x(NaCl) = n(NaCl)/nsol. 100 % = 0,051 mol/13,77 mol = 0,0037 100 % = 0,37 %

FINDING EMPIRICAL and MOLECULAR FORMULAS – CALCULATION PROBLEMS

1. Mesitylene, a hydrocarbon that occurs in small amounts in crude oil, has an empirical formula of
C3H4. The experimentally determined molar mass of this substance is 121 g/mol.
What is the molecular formula of mesitylene?

2. Find the empirical formula of a compound using this data: 36.5 % Na, 25.4% S and the rest is
oxygen. Ar(Na) = 23 Ar(S) = 32 Ar(O) = 16

3. Ascorbic acid (vitamin C) contains 40.92% C, 4.58% H, and 54.5% O by mass. What is the
empirical formula of ascorbic acid?

4. Ethylene glycol, the substance used in automobile antifreeze, is composed of 38.7% C, 9.7% H,
and 51.6% O by mass. Its molar mass is 62.1 g/mol.
a) What is the empirical formula of ethylene glycol?
b) What is its molecular formula?

5. Sample of methyl benzoate, a compound used in the manufacture of perfumes, is found to

contain 3.758 g of carbon, 0.316 g of hydrogen, and 1.251 g of oxygen. What is the empirical
formula of this substance?