CHEMISTRY

DETERMINATION OF STRUCTURES OF ORGANIC COMPOUNDS----

EMPIRICAL, MOLECULAR AND STRUCTURAL FORMULAE.

Definition of Terms

Formula: This is the symbolic representation of chemical substances.

Examples,

Name of compounds Chemical Formula

Sodium chloride NaCl

Sulphuric acid H2SO4

Potassium nitrate KNO3

Empirical formula: This indicates the simple ratio of each element present in one molecule
of the compound. It tells us

a. The component elements in a molecule of the compound

b. The ratio in which these elements are combined together, ie the mole ratio.

For instance, in water (H2O), hydrogen (H) and oxygen (O) are present in the ratio of 2:1, in
ammonia (NH4), nitrogen (N) and hydrogen (H) are in the ratio of 1:4 etc.

Mole ratio (Number of mole) of each component element in a compound is

𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑏𝑦 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑚𝑒𝑛𝑡

𝑅𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

Or 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑚𝑒𝑛𝑡

Molecular formula: It indicates the actual number of atoms present in one molecule of the
compound. Example: The compound butene has a molecular formula of C4H8 and empirical
formula of CH2. The actual number of atoms present in the compound is 12 for its molecular
formula but empirical formula is 3. Again, the actual number of atoms present in one molecule
of H2O is 3 and in NH3 is 4 etc.

Structural formula: It indicates the relative arrangement of each atom present in one molecule
of the compound. Eg the correct relative arrangement of each atom present in

H2O is H-O-H

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Determination of Empirical and Molecular formulae

If we know the number of atoms in a compound, and its molecular mass, then we can work out
its molecular formula. This is the actual formula of the compound. While empirical formula of
a compound gives the whole number ratio of the component elements, molecular formula gives
the exact number of moles of atoms of the component elements in one mole of the compound.

For eg, the molecular formula of benzene is C6H6. This shows us that the molecule
contains 6 carbon atom and 6 hydrogen atoms. The molecular formula of C 6H6 is different to
its empirical formula which is CH.

Two or more compounds can have same empirical formula but different molecular formula.

For instance the molecular formula of ethyne is C 2H2 and its empirical formula is CH
just like that of benzene which is CH too. One can work out the molecular formula from the
empirical formula if the relative molecular mass or molar mass of the substance is known.

CALCULATING EMPIRICAL FORMULAS

There are steps to take for easy calculations of empirical formulas

❖ Step 1: If the element is given in a percent, assume 100 g.

❖ Step 2: Convert the mass of each element to moles using the molar mass.
❖ Step 3: Divide each mole value by the smallest mole value.
❖ Step 4: If CLOSE, Round to the nearest whole number.
1. If answer is not close to a whole number, you will need to multiply by a factor of 2 or 3.
2. If answer ends with 0.5, multiply by 2.
3. If answer ends with 0.3 or 0.6, multiply by 3.
4. You MUST multiply EACH element by the factor!
❖ Step 5: Write Empirical Formula using answers as the subscripts.

CALCULATING MOLECULAR FORMULAS

Steps to take while calculating the molecular formulas are:

❖ Step 1: Find the molar mass of the empirical formula.

❖ Step 2: Divide the molecular mass by the empirical mass (big number by small
number).
❖ Step 3: Multiply answer by each subscript in the empirical formula to get molecular
formula.

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Table and Calculations

Table 1: Examples of empirical and molecular formula

Compound Empirical formula Molecular formula Number of moles

Water H2O (H2O)n = H2O n= 1

Hydrogen peroxide HO (HO)n = H2O2 n= 2

Ethyne CH (CH)n = C2H2 n= 2

Benzene CH (CH)n = C6H6 n= 6

Nitrogen monoxide N2O (N2O)n =N2O n= 1

CALCULATIONS

1. A sample placed in a mass spectrometer gave a parent ion corresponding to a relative

molecular mass of 44. Analysis of a sample of the oxide showed that 2.2g of it contained
1.4g of Nitrogen atoms and 0.8g of oxygen atoms. Find the molecular formula of the
oxide. (N=14, O= 16)

Solutions

Step1: Calculate the number of mole of each of the element

𝑅𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

Number of moles =
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑚𝑒𝑛𝑡

Work out the number of moles of Nitrogen and Oxygen atoms.

1.4𝑔
Number of moles of N2 atom = 14𝑔/𝑚𝑜𝑙 = 0.1mol

0.8𝑔
Number of moles of O2 atom = 16𝑔/𝑚𝑜𝑙 = 0.05mol.

Step 2: Divide each by the smallest value (0.05)

0.1
For N2 = 0.05
=2

0.05
For O2 = 0.05 = 1

Therefore we have N2O

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From the above illustrations, it shows that there is twice as much N2 as O2 i.e the ratio is 2mol
Nitrogen atom to 1mol of Oxygen atoms. This ratio gives us the empirical formula of the
compound. In this case it is N2O.

One should not think that we have proved that the compound is N2O vividly because
we would get exactly the same empirical formula if the molecular formula was N4O2, N6O3,
N8O4 etc. However, the mass spectrum evidence tells us that the relative molecular mass is
44g/mol. Therefore, let’s check which of the compounds above fits in with the molar mass of
44g/mol.

Starting with the simplest formula which is N2O

For nitrogen (N2) = (14*2)g/mol = 28g/mol

For oxygen (O) = 16g/mol

N2O = (28+16)g/mol = 44g/mol

With this, we have proved that the molecular formula is N2O.

2. An organic compound has the following percentage composition C = 40%, H = 6.7%

and O = 53.3%. Calculate the empirical formula of the compound. (C=12, H= 1 and O=
16)

Solutions

Step 1: Find the number of mole for each of the element

𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛
Number of moles =
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
40
For Carbon 12
= 3.33

6.7
For Hydrogen = 6.7
1
53.3
For Oxygen = 3.33
16

Step 2: Divide each by the smallest value (3.33)

3.33
For Carbon = =1
3.33
6.7
For Hydrogen = = 2.02
3.33

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 3.33
For Oxygen = =1
3.33

The empirical formula of the compound is CH2O.

3. Compound containing carbon and hydrogen was found to contain 92.31% carbon; the
mole weight of the compound is 78. Calculate the mole formula. (C=12, H=1)

Solutions

Step 1: Find the number of mole for each of the element

𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛
Number of mole =
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

The compound is made up of carbon and hydrogen, and since carbon is 92.31%, it means
that hydrogen will be 7.69% (100-92.31)%.

92.31
For Carbon = = 7.69
12
7.69
For Hydrogen = = 7.69
1

Step 2: Divide each value by 7.69

7.69
For Carbon = =1
7.69
7.69
For Hydrogen = =1
7.69

The empirical formula is CH

Step 3: Find the molecular formular by calculating the number of moles of the compound (CH)

Number of mole (n) =

𝑚𝑜𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
𝑒𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑤𝑒𝑖𝑔ℎ𝑡.

78 78
= = =6
(12+1) 13

Again, Molecular formula = number of moles * empirical formula

Molecular formula = n* empirical formula

= 6(CH) = C6H6 (Benzene)

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 4. Find the empirical formula of a compound which on analysis yields the following as
the reacting masses Carbon 2.0g, Hydrogen 0.34g and Oxygen 2.67g. From your
result, find the molecular formula of the compound if its relative molecular mass is 60.
(C =12, H =1 and O = 16)

Solutions

Step 1: Find the number of moles for each of the elements (C, H and O)

𝑅𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑚𝑎𝑠𝑠
Number of moles =
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
2.0
For C = = 0.17
12
0.34
For H2 = =2
1
2.67
For O2= = 0.17
16

Step 2: Divide each by the smallest value (0.17)

0.17
For C = =1
0.17
2
For H2 = =2
0.17
0.17
For O2 = =1
0.17

From the above calculation, the empirical formula of the compound is CH2O

Step 3: Find the molecular formula by calculating the number of mole of the compound
(CH2O).

𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 60 60
Number of mole (n) = = = =2
𝐸𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 12+2+16 30

Again, Molecular formula = number of mole * empirical formula

Therefore Molecular formula = 2(CH2O) = C2H4O2 or CH3COOH (Methanoic acid).

5. Determine the empirical formula of an oxide of nitrogen containing 70% of oxygen if

the relative molecular mass of the oxide is 92. Deduce its molecular formula. (N=14
and O=16)

Solutions

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Step 1: To calculate the number of mole of each of the elements.

The compound is made up of nitrogen and oxygen, and since oxygen is 70%, it means that
nitrogen will be 30%.

𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛
Number of mole =
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
30
For Nitrogen= = 2.1
14
70
For Oxygen= = 4.38
16

Step 2: Dividing with smallest value (2.1)

2.1
For Nitrogen = =1
2.1
4.38
For Oxygen = =2
2.1

So the ratio of Oxygen to Nitrogen is 2:1 therefore the empirical formula is NO2

Step 3: To calculate the molecular formula by calculating the number of the mole of the
compound (NO2).

𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 92 92 92

Number of mole (n) = = = = =2
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 14+(16)2 14+32 46

The molecular formula = number of mole * empirical formula

Therefore molecular formula = 2(NO2) = N2O4.

6. 6g of metal M react completely with 23.66g of chlorine to form 29.66g of the metallic
chloride. Find the empirical formula of the metallic chloride (M= 27 and Cl= 35.5).

Solutions

Step 1: Calculate the number of moles for each of chlorine and the metal

𝑅𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑚𝑎𝑠𝑠
Number of mole =
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
6
For metal M = = 0.222
27
23.66
For chlorine = = 0.666
35.5

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Step 2: Dividing with smallest value (0.222)

0.222
=1
0.222
0.666
=3
0.222

So, the ratio of metal M to Chlorine is 1:3

Therefore, the empirical formula of the metallic chloride is MCl3

7. A material is found to be composed of 38.7% Carbon, 51.6% Oxygen, and 9.7%

Hydrogen. By other means, it is known that the molecular weight/mass is 62.0.
Calculate the empirical and molecular formula for the compound.

Solutions.
Step 1: Calculate the number of moles each of carbon, oxygen and hydrogen

𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑚𝑎𝑠𝑠
Number of mole =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
38.7
For carbon = = 3.23mol
12
51.6
For oxygen = = 3.23mol
16
9.7
For hydrogen = = 9.7mol
1

Step 2: Divide all the moles by the smallest one (3.23)

3.23
For carbon = =1
3.23
3.23
For oxygen = =1
3.23
9.7
For hydrogen = =3
3.23

So the empirical formula is CH3O.

Calculating the molecular formula

Step 1: To calculate the molecular mass of the empirical formula (CH3O)

C = 12*1 = 12 g/mol

H = 1*3 = 3 g/mol

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O = 16*1 = 16 g/mol

Molecular mass of CH3O = 12+3+16 = 31g/mol

Therefore the molecular mass of the empirical formula = 31 g/mol

𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
Number of mole (n) =
𝐸𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑚𝑎𝑠𝑠

62
= =2
31

2* (CH3O) = C2H6O2

Empirical formula Molecular formula

8. Calculate the molecular formula of the compound whose molecular mass is 60.0g and
the empirical formula is CH4N.

Solutions

Empirical weight of CH4N = 12+1(4)+14 = 30.0g

Actual weight = 60.0g

𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 60
Number of moles (n) = = =2
𝐸𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 30

So multiplying the empirical formula by 2 we have

2* (CH4N) = C2H8N2

Empirical formula Molecular formula

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Exercises

A. Find the empirical formula of the following compounds from their percentage
composition by mass
❖ N = 26.17%; H = 7.48%; Cl = 66.35%
❖ Ca = 71.43%; O = 28.57%
❖ Ag = 63.53%; N = 8.23%; O = 28.24%
❖ Na = 32.40%; O = 45.07%; S = 22.53%

Note (N = 14, H = 1, Cl = 35.5, Ca = 40, O = 16, Ag = 108, Na = 23, S = 32)

B. If the relative molecular mass of CH2O is 60, calculate the number of mole of the
compound. (C = 12, H = 1, O = 16).
C. What is the empirical and molecular formula of benzene?

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