Stoichiometry

– Studies the quantitative aspects of chemical reactions

3.1 The Mole
• Unit for amount of substance in terms of the
number of entities (atoms, molecules, ...) in it.
1 mol of entities → # of atoms in 12 g of 12C
1 atom of 12C → 1.99265×10-23 g12C (mass spectrometry)
12 g12C×[1 atom/1.99265×10-23 g12C] = 6.022×1023 atoms
⇒1 mol of entities → 6.022×1023 entities
• Avogadro’s number (NA) – number of entities
per 1 mol → NA = 6.022×1023 /mol

• Conversion between moles and entities • The atomic mass (in amu) of an element is
[1 mol entities/6.022×1023 entities] numerically equal to the mass (in g) of 1 mol
Example: of the element
– 12C → 12 amu 1 mol 12C → 12 g (definitions)
1) How many molecules of water are present – C → 12.01 amu 1 mol C → 12.01 g
in 2.7 mol of water? – H → 1.008 amu 1 mol H → 1.008 g
2) How many atoms of hydrogen are present – O → 16.00 amu 1 mol O → 16.00 g
in 2.7 mol of water? • The molecular (formula) mass (in amu) of a
compound is numerically equal to the mass
 6.022 × 10 23 molec. H 2O 
2.7 mol H 2O  = 1.6 × 10 24 molec. H 2O (in g) of 1 mol of the compound
 1 mol H O 
2
– CO2 → 44.01 amu 1 mol CO2 → 44.01 g
 2 atoms H 
1.6 × 10 24 molec. H 2O  = 3.3 × 10 24 atoms H ⇒1 mol of a substance has a fixed mass (can be used
 1 molec. H 2O  to measure moles of substances by weighing them)

Molar Mass (M) • M is numerically equal to the atomic,

molecular, or formula mass of the substance
• Mass of a substance per 1 mol of its entities
– For elements, M = atomic mass (from per. table)
– element → atoms (or molecules for H2, O2, P4, ...)
– For molecular compounds and molecular
– molecular compound → molecules elements, M = molecular mass
– ionic compound → formula units – For ionic compounds, M = formula mass
• Units of M → g/mol ⇒ For compounds and molecular elements, M
• M = mparticle× NA equals the sum of the molar (atomic) masses of the
elements in the formula
Example:
Example:
What is the molar mass of 1H, if the mass of 1 Calculate the molar masses of O2 and Li2O.
atom 1H is 1.673×10-24 g? M(O2) = 2×16.00 = 32.00 g/mol
M = 1.673×10-24g × 6.022×1023 /mol = 1.007 g/mol M(Li2O) = 2×6.941 +1×16.00 = 29.88 g/mol

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• M can be used as a conversion factor • Conversion between moles (n) and masses
• Conversion between moles (n) and mass (m) (m) of elements
m=n×M ↔ n = m/M Example:
What is the mass of 1.221 mol Kr?
m = 1.221 mol × 83.80 g/mol = 102.3 g
Example:
How many moles of atoms are present in
1.23 g of Kr?

 1 mol Kr 
1.23 g Kr ×  . × 10−2 mol Kr
 = 147
 83.80 g Kr 

• Conversion between moles (n) and masses • Conversion between masses and number of
entities of elements and compounds
(m) of compounds (same as for elements)
Example:
Example:
Calculate the number of CO2 molecules and
Calculate the number of moles of urea, oxygen atoms in 15.8 g of CO2.
(NH2)2CO, in 2.3×105 kg of this compound.
M(CO2) = 12.01 + 2×16.00 = 44.01 g/mol
M = 2×14.00 + 4×1.008 + 1×12.01 + 1×16.00 = 60.04 g/mol
 1 mol CO2  6.022 × 1023 molec. CO2 
 103g urea   1 mol urea  15.8 g CO2   
2.3×105 kg urea ×   44.01 g CO2  1 mol CO2
×  
 1 kg urea   60.04 g urea  = 2.16 × 1023 molec. CO2

= 3.8 ×106 mol urea  2 atoms O 

2.16 × 1023 molec. CO2   = 4.32 × 1023 atoms O
 1 molec. CO2 

• Conversion between masses of compounds

and masses of their elements using chemical
formulas (The subscripts in formulas refer to
individual atoms as well as to moles of atoms)
Example: What is the mass of H in 5.00 g CH4?
CH4 → M = 1×12.01 + 4×1.008 = 16.04 g/mol
H → M = 1.008 g/mol
 1 mol CH 4   4 mol H 
5.00 g CH 4 ×   × ×
 16.04 g CH 4   1 mol CH 4 
 1008
. g H
×  = 126
. gH
 1 mol H 

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Mass Percentage Composition Mass% of element
=
• Percentage by mass of each element in a
 (# atoms of element in formula )( M of element ) 
compound   × 100%
 ( M of compound ) 
Mass% = [melement/mcompound]×100%
• Calculation of Mass% from chemical Example:
formulas Calculate the Mass% of O in CO2.
– Consider 1 mol of a compound CO2 → M = 1×12.01 + 2×16.00 = 44.01 g/mol
mcomp = M of comp O → M = 16.00 g/mol
melem = (# moles of elem in 1 mol of comp)×(M of elem)  2 × 16.00 g/mol 
Note: The # of moles of the element in 1 mol of the Mass% O =   × 100% = 72.71%
compound equals the # of atoms of the element in the  44.01 g/mol 
formula of the compound

• Calculation of Mass% from chemical 3.2 Determination of Chemical Formulas

analysis
• Molecular formulas – numbers of atoms of
Example: each element in a molecule
Calculate the mass percentage of C in • Empirical formulas – relative numbers of
nicotine, if analysis shows that 5.00 g of
atoms of each element using the smallest
nicotine contain 3.70 g C, 0.44 g H and
0.86 g N. whole numbers
Example:
 3.70 g C  acetic acid → C2H4O2 (MF) → CH2O (EF)
Mass% C =   × 100% = 74.0%
 5.00 g nicotine  formaldehyde → CH2O (MF) → CH2O (EF)
glucose → C6H12O6 (MF) → CH2O (EF)

Determining Empirical Formulas Example:

• Elemental analysis – gives the masses of the • Determine the EF of nicotine, if the mass%
elements in a given mass of the compound or of C, H and N in it are 74.0, 8.7 and 17.3 %,
the Mass% composition
respectively.
• EF from Mass% data
1. Consider 100 g of the compound
1. Consider 100 g nicotine
2. The masses of the elements equal their mass% 2. 74.0 g C, 8.7 g H, 17.3 g N
3. Convert the masses of the elements to moles 3. Convert masses to moles:
4. Determine the relative number of moles (mol ratio)
74.0 g C×(1 mol C/12.01 g C) = 6.16 mol C
5. Simplify the mole ratio to whole numbers
8.7 g H×(1 mol H/1.008 g H) = 8.6 mol H
• EF from mass data
– Omit steps 1 and 2 above
17.3 g N×(1 mol N/14.01 g N) = 1.23 mol N

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4. Mol ratio:
Determining Molecular Formulas
6.16 mol C : 8.6 mol H : 1.23 mol N
5. Simplify the mole ratio: • The MF is a whole-number multiple of the EF
(divide by the smallest number, and if necessary, ⇒ M = MEF × n
multiply by a factor to get whole numbers)
6.16/1.23 = 5.01 ≅ 5 – M → molar mass
8.6/1.23 = 7.0 ≅ 7 – MEF → EF mass
1.23/1.23 = 1.00 ≅ 1 – n → whole number (number of EFs per
→ simplest whole-number ratio: molecule)
5 mol C : 7 mol H : 1 mol N ⇒ n = M/MEF
→ EF: • Determining MFs from EFs and molar masses
C5H7N

Example: Combustion Analysis

• A method for elemental analysis of combustible
• The empirical formula of nicotine is C5H7N organic compounds through their combustion
and its molar mass is 162.23 g/mol. MF = ? in excess O2
MEF → 5×12.01+7×1.008+1×14.01 = 81.12 g/mol – The C in the sample is converted to CO2 which
is absorbed in a NaOH absorber and weighed
M 162.23 g/mol – The H in the sample is converted to H2O which
n= = = 2.000 ≅ 2 is absorbed in a P4O10 absorber and weighed
M EF 81.12 g/mol
– If a third element (O, N, …), it passes through
the absorbers
⇒MF = 2 × EF
1 mol C from the sample → 1 mol CO2
MF →C10H14N2 2 mol H from the sample → 1 mol H2O

Example:  1 mol CO 2   1 mol C 

0.519 g CO 2 ×  × ×
When 0.236 g aspirin is burned in excess O2,  44.01 g CO 2   1 mol CO 2 
0.519 g CO2 and 0.0945 g H2O are formed.  12.01 g C 
Determine the mass % of C, H and O in ×  = 0.142 g C
 1 mol C 
aspirin.  1 mol H 2O   2 mol H 
0.0945 g H 2O ×  × ×
 18.02 g H 2O   1 mol H 2O 
¾Calculate the masses of C and H in the sample
 1.008 g H 
based on the masses of CO2 and H2O: ×  = 0.0106 g H
 1 mol H 
¾Calculate the mass of O by subtracting the
masses of C and H from the total mass of the
sample 0.236-0.142-0.0106=0.084 g O

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 3.3 Chemical Equations
 0.142 g C 
%C=   × 100% = 60.0% • Represent chemical reactions
 0.236 g sample  Reactants → Products
 0.0106 g H  • Skeletal equations – show identities of
%H=   × 100% = 4.48% reactants and products
 0.236 g sample 
 0.084 g O  H2 + O2 → H2O
%O=   × 100% = 35.5% • Law of conservation of mass
 0.236 g sample 
– Atoms are neither created nor destroyed (they
only change bonding partners)
The empirical formula can be determined from
the percentage composition in a subsequent step – Same atoms are present in the reactants as in the
products

• Balanced chemical equations – The stoichiometric coefficients can be treated as

– same number of atoms of each element appear relative number of moles of reactants and
on each side of the equation products
– stoichiometric coefficients – needed to balance – Physical state symbols
the equations • (s) solid; (l) liquid; (g) gas; (aq) aqueous solution

2H2 + O2 → 2H2O 2K(s) + 2H2O(l) → 2KOH(aq) + H2(g)

– Microscopic view
Balancing Chemical Equations
(2 molec. H2 + 1 molec. O2 → 2 molec. H2O)
• Balancing by inspection (only simple cases)
– Macroscopic view
– Change stoichiometric coefficients only
(2 mol H2 + 1 mol O2 → 2 mol H2O) – Never change subscripts in formulas
(4.032 g H2 + 32.00 g O2 → 36.032 g H2O) – Never add other substances to the equation

• Systematic method Example: Write the balanced equation for the

1. Write the skeletal equation combustion of ethane, C2H6, to carbon dioxide
2. Balance one element at a time using coefficients and liquid water.
– Start with the elements in the most complex substance
and finish with those in the least complex one C2H6 + O2 → CO2 + H2O skeletal
– Alternatively, start with the element present in the
fewest number of formulas and finish with the element C2H6 + O2 → 2CO2 + H2O for C
present in the greatest number of formulas
C2H6 + O2 → 2CO2 + 3H2O for H
– Use fractional coefficients if necessary
3. If necessary multiply the whole equation by a C2H6 + (7/2)O2 → 2CO2 + 3H2O for O
factor to clear the fractional coefficients multiply eq. by 2
4. Verify that the equation is balanced and the 2C2H6 + 7O2 → 4CO2 + 6H2O
coefficients are the smallest whole numbers
5. Specify physical states 2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l)

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 – Often polyatomic ions can be treated as single 3.4 Calculating Amounts of Reactants
entities and Products
Example: Balance the following skeletal eq. Stoichiometric Equivalences
in aqueous solution: • Balanced chemical equations contain definite
Co(NO3)3 + (NH4)2S → Co2S3 + NH4NO3 stoichiometric relations between reactants and
products → stoichiometric mole ratios
→balance Co and S:
Example: 2H2 + O2 → 2H2O
2Co(NO3)3 + 3(NH4)2S → Co2S3 + NH4NO3 2 mol H2 ⇔ 1 mol O2
stoichiometric
→ balance NH4 and NO3: 2 mol H2 ⇔ 2 mol H2O equivalences
1 mol O2 ⇔ 2 mol H2O
2Co(NO3)3 + 3(NH4)2S → Co2S3 + 6NH4NO3
1 mol O2 / 2 mol H2
→add physical state symbols: stoichiometric
2 mol H2O / 2 mol H2 mole ratios
2Co(NO3)3(aq) + 3(NH4)2S(aq) → Co2S3(s) + 6NH4NO3(aq) 2 mol H2O / 1 mol O2

Mole-to-Mole Conversions • Stoichiometric conversion factors are reaction

specific
• Conversion method
– The mole ratios are used as conversion factors Example: Calculate the amount of O2 needed to
produce 3.5 mol H2O by combustion of methane
(mol given)×(mole ratio) = (mol required)
(CH4).
Example: Determine the number of moles of → balanced equation:
water produced from 3.4 mol O2. CH4 + 2O2 → CO2 + 2H2O
→ balanced equation: 2H2 + O2 → 2H2O → mole ratio (conversion factor):
→ mole ratio (conversion factor): [2 mol H2O/1 mol O2] 2 mol O2 ⇔ 2 mol H2O
[2 mol O2/2 mol H2O]
 2 mol H 2O   2 mol O 2 
3.4 mol O 2 ×   = 6.8 mol H 2O 3.5 mol H 2O ×   = 3.5 mol O 2
 1 mol O 2   2 mol H 2O 

Mass-to-Mass Calculations Example: Calculate the mass of oxygen needed to

• Conversion method completely burn 5.4 kg of butane (C4H10).
→ balanced equation:
2C4H10 + 13O2 → 8CO2 + 10H2O
→ mole ratio: [13 mol O2/2 mol C4H10]
→ molar masses:
C4H10 → 58.1 g/mol O2 → 32.0 g/mol
 10 3 g C4 H 10   1 mol C4 H 10 
5.4 kg C4 H 10 ×   ×   ×
 1 kg C4 H 10   58.1 g C4 H 10 
 13 mol O 2   32.0 g O 2 
  ×   = 1.9 × 104 g O 2 = 19 kg O 2
 2 mol C4 H 10   1 mol O 2 

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Reaction Yield • Reasons for the difference between actual
• Theoretical yield - the maximum amount of and theoretical yield
product that can be expected from a given – incomplete reaction
amount of reactant – loss of product
• Actual yield - the actual amount of product – side reactions
isolated in a reaction
Actual Yield ≤ Theoretical Yield
• Percentage yield:
Actual Yield
% Yield = × 100%
Theoretical Yield

Example: Calculate the theoretical yield of Example: Calculate the percentage yield of
carbon dioxide produced by the combustion of carbon dioxide, if the combustion of 25.0 g
25.0 g propane (C3H8) in excess oxygen. propane in excess oxygen yields 48.5 g carbon
→balanced equation: dioxide.
C3H8 + 5O2 → 3CO2 + 4H2O → theoretical yield (from prev. problem): 74.9 g CO2
→mass-to-mass conversion: → side reaction (consumes some of the propane):
2C3H8 + 7O2 → 6CO + 8H2O
 1 mol C3 H8   3 mol CO2 
25.0 g C3 H8 ×  × × → actual yield: 48.5 g CO2
 44.09 g C3 H8   1 mol C3 H8  → percentage yield:
 44.01 g CO2  48.5 g CO 2
×  = 74.9 g CO2 → Theor . Yield % Yield = × 100% = 64.8%
 1 mol CO2  74.9 g CO 2

Limiting Reactants Example: Identify the limiting reactant in the

• Reactants present in equivalent amounts reaction of 5.0 mol H2 with 3.0 mol N2, and
• All reactants are consumed at the same time determine the theoretical yield of NH3 in this
• Nonequivalent amounts of reactants reaction.
• One reactant, called limiting reactant, is consumed →balanced equation: 3H2 + N2 → 2NH3
before the others
→calculate the theoretical yield based on each of the reactants
• The other reactants are in excess and chose the smaller result:
• Limiting reactant
 2 mol NH 3 
• The reaction stops when the limiting reactant is 3.0 mol N 2 ×   = 6.0 mol NH 3
consumed  1 mol N 2 
• Limits the maximum amount of product achievable
(limits the theoretical yield)  2 mol NH 3 
5.0 mol H 2 ×   = 3.3 mol NH 3 → Theor . Yield
• Stoichiometric calculations based on the limiting  3 mol H 2 
reactant give the lowest amount of product smaller amount
compared to calculations based on the other reactants ⇒ H2 is the limiting reactant

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 Example: Calculate the theoretical yield of HNO3  1 mol NO 2   2 mol HNO 3 
in the reaction of 28 g NO2 and 18 g H2O by the 28 g NO 2 ×  × ×
chemical equation:  46.0 g NO 2   3 mol NO 2 
3NO2(g) + H2O(l) → 2HNO3(l) + NO(g).  63.0 g HNO 3 
×  = 26 g HNO 3 → Theor . Yield
→Calculate the theoretical yield based on each of the reactants  1 mol HNO 3 
and chose the smaller result: smaller amount
 1 mol H 2 O   2 mol HNO 3 
18 g H 2O ×  × × ⇒The smaller amount of product results
 18.0 g H 2O   1 mol H 2 O 
from the calculation based on NO2
 63.0 g HNO 3  ⇒NO2 is the limiting reactant and 26 g HNO3
×  = 130 g HNO 3
 1 mol HNO 3  is the theoretical yield

3.5 Solution Stoichiometry • Preparation of solutions with known molarity

– Transfer a known mass of solute in a volumetric
• Solutions – homogeneous mixtures flask
– Solvent and solute(s) – Dissolve in small amount of water
– Add water to the mark
– Solution concentration
Molarity (M)
• Measure of the solute concentration
 amount of solute (mol)  n
M =  or M=
 volume of solution (L)  V

• Units – molar (M) 1 M = 1 mol/L

Example: • Molarity as a conversion factor

Calculate the molarity of a solution prepared Example:
by dissolving 5.33 g NaOH in water using a Calculate the mass of NaOH in 2.50 L of
100.0 mL volumetric flask. 1.33 M NaOH solution.
⇒ convert the mass to moles:
 1.33 mol NaOH   40.00 g NaOH 
 1 mol NaOH  2.50 L 
1L   1 mol NaOH  = 133 g NaOH
5.33 g NaOH ×    
 = 0.133 mol NaOH
 40.00 g NaOH 
Example:
⇒ convert volume to liters: 100.0 mL = 0.1000 L
Calculate the volume of 1.33 M NaOH
⇒ divide moles by solution volume:
solution that contains 5.00 mol NaOH.
0.133 mol NaOH  1L 
= 1.33 mol NaOH/L → 1.33 M NaOH 5.00 mol NaOH × 
0.1000 L solution  = 3.76 L
 1.33 mol NaOH 

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Dilution • Dilution calculations
• Reducing the concentration of the solute by – dilution doesn’t change the total # of moles of
solute in the solution
adding more solvent
n = M×V n d = nc Md×Vd = Mc×Vc
• Stock solutions – concentrated solutions used
to store reagents Example:
• Dilution Procedure Calculate the molarity of a solution prepared
by dilution of 5.00 mL 2.0 M HCl stock
– Use a pipette to measure a small volume of the solution to 100.0 mL.
concentrated solution and transfer it to a
volumetric flask
M c × Vc 2.0 M × 5.00 mL
– Add solvent to fill the volumetric flask to the Md = = = 0.10 M
mark Vd 100.0 mL

Stoichiometric calculations in solution Example:

– For a reaction involving substances A and B What volume of 0.0836 M H2SO4 solution will
react completely with 16.4 mL 0.255 M KOH.
⇒ balanced equation:
2KOH(aq) + H2SO4(aq) → K2SO4(aq) + 2H2O(l)
⇒ mole ratio: [1 mol H2SO4/2 mol KOH]

 0.255 mol KOH   1 mol H 2SO4 

16.4 × 10−3 L ×   ×  2 mol KOH 
 1L   
 1L  −3
×  = 25.0 × 10 L = 25.0 mL
 0.0836 mol H 2 SO 4 

Limiting reactant problems in solution ⇒ calculation based on HCl:

Example:  0.15 mol HCl   1 mol H2   2.02 g H2 
2.0 L ×   ×  2 mol HCl  ×  1 mol H 
What mass of H2 gas can be produced by the  1L     2 
reaction of 2.5 g Zn with 2.0 L 0.15 M HCl = 0.30 g H2
solution. The other product is ZnCl2(aq).
⇒ balanced equation: ⇒ calculation based on Zn:
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)  1 mol Zn   1 mol H 2   2.02 g H 2 
2.5 g Zn ×  × × 
⇒ mole ratios: [1 mol H2/2 mol HCl]  65.4 g Zn   1 mol Zn   1 mol H 2 
[1 mol H2/1 mol Zn] = 0.077 g H 2 ← smaller amount
⇒ Calculate the mass of H2 produced based on ⇒ The calculation based on Zn yields less
both reactants and choose the smaller amount product so Zn is the limiting reactant