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Empirical Formula- the simplest whole number ratio

of # of atoms of elements in a compound


E.g HO 1 hydrogen, 1 oxygen
This may or may not be the true or molecular
formula
Molecular Formula- represents the actual # of atoms
of elements in a unit of the compound
E.g H2O2 2 hydrogen, 2 oxygen atoms

Compound

Molecular
Formula

Empirical
Formula

Glucose
Octane
Copper(ii) chloride
Ethane

C6H12O6
C8H18
CuCl2
C2H6

CH2O
C4H9
CuCl2
CH3

Empirical Formula
Calculations to find the simplest formula incorporate this rhyme:

% to mass
Mass to mole
Divide by small
Multiply till whole

Calculating Empirical Formulas Using % composition


Steps to find subscripts ...
STEP 1. Find the mass of each element in the compound (i.e. Convert % element into mass of element by
assuming a 100 g mass sample)
STEP 2. Find the # of moles of each element (n = m/M)
STEP 3. Express the mole ratio between the elements in terms of small whole numbers. (i.e. Divide by the
smallest mole value)
STEP 4. Find the whole number ratios (if #s differ only slightly from whole #s round off, else, multiply by small
whole # to make all subscripts whole #s)
STEP 5 Use these numbers as subscripts to determine the empirical formula
Example 1: The chlorofluorocarbon Freon-12 is 9.90% carbon, 58.6% chlorine, and 31.5% fluorine by
mass. What is the empirical formula of freon-12?
Step 1: Convert % element into mass of element by assuming a 100 g sample mass
C: 9.90% X 100.0 g = 9.90 g
Cl: 58.6% X 100.0 g = 58.6 g
F: 31.5 % X 100.0 g = 31.5 g
STEP 2. Find the # of moles of each element
C: 9.90 g / (12.0 g/mol) = 0.825 moles of C
Cl: 58.6 g/(35.5 g/mol) = 1.65 moles of Cl
F: 31.5 g/ (19.0 g/mol) = 1.66 moles of F
STEP 3. Express the mole ratio between the elements in terms of small whole numbers. (i.e. Divide by the
smallest mole value)
C: 0.825 mol/0.825 mol = 1.00
Cl: 1.65 mol/ 0.825 mol = 2.00
F: 1.66 mol/ 0.825 mol = 2.01
Ratio: 1C: 2Cl:2F
Empirical Formula: CCl2F2
A chart form may help to organize work! (see below)
One approach to determining the empirical formula is to chart the information...

Element

% or g
(assume 100 g)

Molar Mass
(g/mol)

# moles
(mol)

Ratio of moles

Subscripts
(whole # ratio)

X
Y
Z

Example 2: A compound contained 29.08 % Na, 40.58 % S, and 30.34 % O. Find its Empirical Formula.
Suppose 100 g sample
Element
% or
Mass ( g)
Na

29.08g

M
(g/mol)

n=m/M
( mol)

Ratio of Moles

Subscripts
(whole # ratio)

22.99g/mol

29.08/22.99
= 1.266 mol
40.58/32.06
= 1.266 mol
30.34/16.00
= 1.896 mol

1.266= 1
1.266
1.266 = 1
1.266
1.896 = 1.5
1.266

1 x 2=2

40.58g

32.06g/mol

30.34g

16.00g/mol

1 x 2=2
1.5 x 2=3

The formula is Na2S2O3 or Sodium thiosulfate


Example 3: What is the empirical formula of a compound which is made up of 26.52 % Cr,
24.52 % S and the rest % O
Suppose a 100 g sample

Element

% or
Mass (g)

Molar Mass
(g/mol)

# moles
(mol)

Ratio of moles

Subscripts
(whole # ratio)

Cr

26.52 g

52.0 g/mol

0.51 mol

0.51/0.51 = 1

1x2=2

24.52 g

32.07 g/mol

0.77 mol

0.77/0.51=1.51

1.5x2=3

48.96 g

16.00 g/mol

3.06 mol

3.06/0.51 = 6

6x2=12

times by 2 to get whole #


Therefore the empirical formula will be Cr2S3O12

True formula can only be found if the true molar mass is given (since it depends on the actual
number of atoms)
In some cases, the empirical and molecular formulas are identical.
In other cases, the molecular formula is a whole-number multiple of the empirical formula.
If you know the molar mass simply divide it by the empirical mass to obtain a ratio by which the
subscripts in the empirical formula can be multiplied in order to obtain the molecular formula (factor
coefficient)

Factor coefficient, X

= Experimental Molar mass


Empirical formula Molar mass
Then multiplying the formula by the ratio

Example 1: The empirical formula of a compound was found to be CH2. Its molecular mass was also found to be
42 g/mol. What is its molecular formula?
Step 1 Determine the empirical formula
already done for you in this case
Step 2 Determine the total molar mass of the empirical formula
1 X C = 12.01 g/mol
2 X H = 2.02 g/mol
14.02 g/mol
Step 3 Divide the molar mass by the empirical formula molar mass
Experimental Molar mass
= Factor coefficient
Empirical formula molar mass
42 g/mol
= 3.0
14.02 g/mol
This tells us the coefficient by which to multiply each of the subscripts in the empirical formula
multiply subscripts by 3 CH2 C1X3H2X3 C3H6
Example 2: Chemical analysis reveals that a compound is 28.64% sulphur and 71.36% bromine. The molar mass
of the compound is 223.94 g/mol. What is its molecular formula?
Suppose a 100 g sample

Element

% or
Mass (g)
28.64 g

Molar Mass
(g/mol)
32.07 g/mol

# moles
(mol)
28.64 g
32.07 g / mol

Ratio of moles

Subscripts
(whole # ratio)

0.8930/0.8931=1

1*

0.8931/0.8930= 1

1*

=0.8930 mol

Br

71.36 g

79.90 g/mol

71.36 g
79.90 g / mol
=0.8931 mol

*Because the subscripts are already whole numbers, you do not need to determine the least common multiple.
The empirical formula is SBr.
Find the molar mass of the empirical formula:

MSBr=1Ms+1MBr
=1(32.07g/mol) + 1(79.90g/mol)=111.97 g/mol
Find the factor coefficient:
x= Experimental Molar Mass = 223.94 g/mol =2
Empirical Formula Molar Mass 111.97 g/mol
Therefore the molecular formula will be 2SBr S1X2 Br1X2 S2Br2
Review Steps:
1. Convert % to mass
2. Find # moles
3. Find the empirical formula
4. Find the molar mass of the empirical formula
5. Find the multiplier
Mtiplier = molecular mass/empirical mass
6. Multiply the multiplier by the empirical formula
NB: Do not round in step 2 or 3

Recall:
Hydrate us a compound that has a specific number of water molecules bound to each formula unit.
These water molecules may have become trapped in a specific arrangement upon crystal formation. (i.e.
calcium sulfate in gypsym incorporates two water molecules into its structure; CaSO42H2O(s).
These molecules are part of the crystal structure and add mass to the solid
When chemists work with ionic compounds in the solid state, they need to know whether these compounds
are hydrates or anhydrous compounds.
Example 1. Consider 1 g sample of magnesium sulfate heptahydrate, MgSO47H2O(s) and 1 g sample of
anhydrous MgSO4(s). Which sample do you think contains more magnesium atoms?
The anhydrous form, since it contains more magnesium sulfate in 1 g sample without any water molecules, and
therefore more magnesium. The hydrated compound contains seven moles of water for every mole of magnesium
sulfate.
Analysis of Hydrated Salts
The amount of H2O in a hydrate can be determined by driving off the water through heating a known mass of
hydrate and then measuring the mass of the anhydrous salt for comparison
Mass of water in sample = (initial mass of hydrate) - (final mass of anhydrous form)
Once this is done, there is enough information to calculate the percentage by mass of water in a hydrate and then
the chemical formula of hydrate.
Example 2. Calculate the percent by mass of water in the hydrate, magnesium sulfate hexahydrate,
MgSO46H2O(s). (answer 50.88%)
To determine how many water molecules are bound to each formula unit of hydrate, you can use mole ratios of
water and anhydrate.
Example 3. A 50.0 g sample of barium hydroxide, Ba(OH)2xH2O(s) contains 27.2 g of Ba(OH)2(s). Calculate the
percent by mass of water in the hydrate, and find the value of x.
Since we will be using mole calculations, we need the molar masses of Barium hydroxide Ba(OH)2 and water, H2O
Molar Mass of Ba(OH)2= M Ba(OH) = 171.35 g/mol
Molar Mass of H2O= MH2O = 18.02 g/mol
2

Mass of water in hydrate= total mass of sample- mass of anhydrate


=50.0 g 27.2 g
=22.8 g
Percent of water in hydrate= mass of water
x 100%
Total mass of sample
=22.8 g x 100% = 45.6%
50.0 g
Number of moles of barium hydroxide, Ba(OH)2:
nBa(OH) =m Ba(OH) =27.2 g
M Ba(OH) 171.35 g/mol
2

= 0.159 mol Ba(OH)2

Number of moles of water, H2O:


nH O =m H O =22.8g
2

= 1.27mol Ba(OH)2

MH O 18.02 g/mol
2

Find the simplest ratio of whole moles of water to moles of anhydrate:

Ratio of moles

Subscripts
(whole # ratio)

Ba(OH)2

0.158 mol/0.159 mol=1

H2O

1.27 mol/0.159 mol=8

Therefore the formula of the hydrate is Ba(OH)28H2O


Finding The molecular Formula of Hydrates:
1. Find mass of anhydrous salt and water (from percentage composition or mass data)
2. Find the # moles of the anhydrous salt
3. Find the # of moles of water
4. Find the ratio of the moles of salt to moles of water
Ratio: moles of water/moles of salt
5. The ratio number is the amount of water Eg CaCl22H2O
Example 4: A hydrated compound contains 76.2 % LaI3 and 23.8% water. Find the molecular formula of the
compound.
Assume 100 g sample.

Compound

LaI3

% or
Mass (g)
76.2 g

Molar Mass
(g/mol)
520 g/mol

# moles
(mol)
76.2g
520 g/mol

Ratio of moles

Subscripts
(whole # ratio)

0.147/0.147=1

1.32/0.147=9

=0.147mol

H2O

23.8 g

18.02 g/mol

23.8g
18.02g/mol

=1.32mol

Therefore formula of hydrate is: LaI39H2O


Example 5: Your sample contained a hydrate of barium hydroxide .Determine the molecular formula of hydrate
from the following experimental data.
Mass of watchglass & sample: 65.0 g
Mass of watch glass: 15.0 g
Mass of sample after heating: 42.2 g
Sample mass before heating
Mass of hydrate= 65.0g-15.0g= 50.0g
Mass anhydrous salt= 42.2-15.0= 27.2g
Mol Ba(OH)2 = 27.2/171.35g/mol= 0.1587
Mass water=50.0g-27.2g= 22.8g
Mol water= 22.8/18.02g/mol = 1.2653 mol
Ratio 0.1587/0.1587= 1 1.2653/0.1587= 8

Therefore molecular formula or barium hydroxide is Ba(OH)28H2O


Analysis of Oxides
Metal oxides can be decomposed by strong heating which drives of the oxygen and leaves behind the metal.
Comparing the mass of the oxide to the resultant metal can allow for determination of the oxides empirical formula.
Carbon-Hydrogen Analysis
In combustion analysis, a known mass of a carbon-containing compound is burned and the mass of the products
(CO2 and H2O) produced can is used to calculate the mass of carbon and hydrogen in the original compound and
hence the empirical formula.
(REFERENCE)
Chemical Analysis
The mass of an element or compound is determined experimentally by using a mass spectrometer. A sample of the
substance is injected into the mass spectrometer and ionized by an electron beam. The resulting cations are then
pulled into the analyzing chamber using a powerful electric field (accelerating plates).

A magnetic field perpendicular to the path of the ion beam is then used to deflect the cations into the detector.
Based on the reading from the detector, a computer displays the results (computer output). A peak is displayed for
all masses observed. If multiple isotopes are present, a separate peak will be displayed for each. In addition, the
height of the peak indicates the abundance of the ion.

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