A 2.00 g sample of impure calcium carbonate (CaCO3) was reacted with 50.0 cm3 of 1.00 mol/dm3 hydrochloric acid (excess). The resulting solution was titrated with 0.500 mol/dm3 sodium hydroxide solution. 25.0 cm3 of NaOH was required for neutralisation.
(a) Write balanced equations for both reactions. [2 marks]
(b) Calculate the percentage purity of CaCO3 in the sample. [5 marks]
(c) Explain why the HCl must be in excess for this method to work. [1 mark]
Step 2: Moles of HCl remaining (unreacted with CaCO3).
From equation 2: n(HCl)remaining=n(NaOH)=0.01250 mol
Step 3: Moles of HCl that reacted with CaCO3.
n(HCl)total=10001.00×50.0=0.0500 mol
n(HCl)reacted=0.0500−0.01250=0.03750 mol
Step 4: Moles of CaCO3 in the sample.
From equation 1: n(CaCO3)=2n(HCl)reacted=20.03750=0.01875 mol
Step 5: Mass of pure CaCO3.
M(CaCO3)=40.1+12.0+3×16.0=100.1 g/mol
m(CaCO3)=0.01875×100.1=1.877 g
Step 6: Percentage purity.
Purity=2.001.877×100%=93.8%
(c) The HCl must be in excess to ensure all the CaCO3 reacts completely. The back-titration then determines the amount of HCl that was not consumed, allowing the amount reacted with CaCO3 to be calculated by difference.
Unit Test 2: Empirical Formula from Combustion Data
An organic compound X contains only carbon, hydrogen, and oxygen. When 0.460 g of X was completely combusted, 0.880 g of CO2 and 0.540 g of H2O were produced.
(a) Determine the empirical formula of X. [5 marks]
(b) If the molar mass of X is 92.0 g/mol, determine its molecular formula. [1 mark]
(c) A student forgets to account for the oxygen in X and assumes X contains only carbon and hydrogen. How would this affect the calculated empirical formula? [2 marks]
Worked Solution
(a) Step 1: Mass of carbon in CO2.
M(CO2)=12.0+2×16.0=44.0 g/mol
m(C)=0.880×44.012.0=0.240 g
Step 2: Mass of hydrogen in H2O.
M(H2O)=2×1.0+16.0=18.0 g/mol
m(H)=0.540×18.02.0=0.0600 g
Step 3: Mass of oxygen by difference.
m(O)=0.460−0.240−0.0600=0.160 g
Step 4: Moles of each element.
n(C)=12.00.240=0.0200 mol
n(H)=1.00.0600=0.0600 mol
n(O)=16.00.160=0.0100 mol
Step 5: Mole ratio.
Divide by the smallest (0.0100):
C:H:O=2:6:1
Empirical formula: C2H6O
(b) Molar mass of empirical formula = 2×12.0+6×1.0+16.0=46.0 g/mol
n=46.092.0=2
Molecular formula: C4H12O2
(c) If oxygen is ignored, the student would calculate:
n(C)=0.0200,n(H)=0.0600
C:H=1:3
The student would get CH3 as the empirical formula, which is incorrect. The mole ratio of C to H alone does not reveal the oxygen content.
At room temperature and pressure (RTP), one mole of any gas occupies 24.0 dm3.
(a) Calculate the volume of carbon dioxide produced when 5.00 g of calcium carbonate reacts with excess hydrochloric acid at RTP. [3 marks]
(b) A student dissolves 4.00 g of NaOH in water and makes up the solution to 250 cm3. Calculate the concentration of the solution in both mol/dm3 and g/dm3. [3 marks]
(c) 50.0 cm3 of 0.100 mol/dm3H2SO4 is diluted to 500 cm3. Calculate the concentration of the diluted solution. [2 marks]
Worked Solution
(a) CaCO3+2HCl→CaCl2+CO2+H2O
n(CaCO3)=100.15.00=0.04995 mol
From the equation, 1 mol CaCO3 produces 1 mol CO2:
n(CO2)=0.04995 mol
V(CO2)=0.04995×24.0=1.20 dm3
(b) M(NaOH)=23.0+16.0+1.0=40.0 g/mol
n(NaOH)=40.04.00=0.100 mol
Concentration (mol/dm3)=0.2500.100=0.400 mol/dm3
Concentration (g/dm3)=0.400×40.0=16.0 g/dm3
(c) Moles of H2SO4 remain constant during dilution:
Chemical accounting: Stoichiometry is like a recipe — the balanced equation tells you exactly how much of each ingredient you need and how much product you’ll get. The mole is the chemist’s dozen.
Why it matters: From manufacturing drugs to calculating fuel efficiency, stoichiometry lets you predict quantities. Errors in stoichiometric calculations can be dangerous or wasteful.
The key insight: The mole concept bridges the gap between atoms (invisible) and grams (measurable) — Avogadro’s number is the conversion factor.
Integration Test 1: Multi-Step Titration and Purity
A sample of impure iron(II) sulphate (FeSO4⋅7H2O) is to be analysed. 5.00 g of the sample was dissolved in dilute sulphuric acid and made up to 250 cm3. 25.0 cm3 of this solution was titrated with 0.0200 mol/dm3 potassium manganate(VII) (KMnO4). The average titre was 22.5 cm3.
(a) Write the balanced ionic equation for the reaction between Fe2+ and MnO4− in acidic medium. [2 marks]
(b) Calculate the percentage of FeSO4⋅7H2O in the impure sample. [5 marks]
(c) Why must the titration be carried out in acidic medium? [1 mark]
Worked Solution
(a) MnO4−+5Fe2++8H+→Mn2++5Fe3++4H2O
(b) Step 1: Moles of MnO4− used.
n(MnO4−)=0.0200×100022.5=4.50×10−4 mol
Step 2: Moles of Fe2+ in 25.0 cm3.
From the equation: n(Fe2+)=5×n(MnO4−)=5×4.50×10−4=2.250×10−3 mol
Step 3: Moles of Fe2+ in 250 cm3 (total solution).
This is impossible, indicating an error. Let me recalculate:
n(MnO4−)=0.0200×0.0225=4.50×10−4 mol
n(Fe2+) in 25.0 cm3=5×4.50×10−4=2.250×10−3 mol
n(Fe2+) total=2.250×10−3×10=0.02250 mol
m=0.02250×277.9=6.253 g
Since this exceeds 5.00 g, the data is inconsistent. For a realistic problem, let me adjust: if the titre were 12.5 cm3:
n(MnO4−)=0.0200×0.0125=2.50×10−4
n(Fe2+) in 25.0 cm3=1.250×10−3
n(Fe2+) total=0.01250
m=0.01250×277.9=3.474 g
% purity=5.003.474×100%=69.5%
(c) The reaction requires H+ ions as a reactant (see the equation). Without an acidic medium, MnO4− would be reduced to MnO2 instead of Mn2+ And the stoichiometry would change. The acid also prevents the formation of insoluble MnO2.
Integration Test 2: Gas Volume + Solution Stoichiometry
Limestone (mainly CaCO3) is analysed by reacting it with acid and collecting the CO2 produced.
2.50 g of limestone was reacted with 100 cm3 of 2.00 mol/dm3HCl. The CO2 gas was collected over water at RTP and measured to have a volume of 520 cm3.
(Vapour pressure of water at RTP = 2.3 kPa; atmospheric pressure = 101 kPa)
(a) Calculate the volume that the dryCO2 would occupy at RTP. [2 marks]
(b) Calculate the percentage of CaCO3 in the limestone sample. [4 marks]
(c) Calculate the concentration of HCl remaining after the reaction. [3 marks]
Worked Solution
(a) The gas collected over water is a mixture of CO2 and water vapour.
Pressure of dry CO2 = Total pressure - Vapour pressure of water
P(CO2)=101−2.3=98.7 kPa
Using Boyle”s law (at constant temperature, P1V1=P2V2) to find volume at atmospheric pressure:
Vdry=101520×98.7=508 cm3=0.508 dm3
(b) n(CO2)=24.0V=24.00.508=0.0212 mol
From CaCO3+2HCl→CaCl2+CO2+H2O:
n(CaCO3)=n(CO2)=0.0212 mol
m(CaCO3)=0.0212×100.1=2.12 g
%CaCO3=2.502.12×100%=84.8%
(c) Moles of HCl reacted:
n(HCl)reacted=2×n(CaCO3)=2×0.0212=0.0424 mol
Moles of HCl initially:
n(HCl)initial=2.00×0.100=0.200 mol
Moles of HCl remaining:
n(HCl)remaining=0.200−0.0424=0.158 mol
C(HCl)remaining=0.1000.158=1.58 mol/dm3
Integration Test 3: Limiting Reagent + Percentage Yield
15.0 g of ethanoic acid (CH3COOH) was reacted with 8.00 g of ethanol (C2H5OH) in the presence of a concentrated sulphuric acid catalyst to produce ethyl ethanoate (CH3COOC2H5) and water. The actual mass of ester obtained was 10.2 g.
(a) Write the balanced equation for the esterification reaction. [1 mark]
(b) Identify the limiting reagent. [3 marks]
(c) Calculate the percentage yield of the ester. [3 marks]
(d) Explain why the percentage yield is less than 100%. [2 marks]
Worked Solution
(a) CH3COOH+C2H5OH⇌CH3COOC2H5+H2O
(b) M(CH3COOH)=2×12.0+4×1.0+2×16.0=60.0 g/mol
n(CH3COOH)=60.015.0=0.250 mol
M(C2H5OH)=2×12.0+6×1.0+16.0=46.0 g/mol
n(C2H5OH)=46.08.00=0.174 mol
From the equation, the mole ratio is 1:1. Since 0.174<0.250ethanol is the limiting reagent.
(c) Theoretical moles of ester = moles of limiting reagent = 0.174 mol
M(CH3COOC2H5)=4×12.0+8×1.0+2×16.0=88.0 g/mol
mtheoretical=0.174×88.0=15.3 g
% yield=15.310.2×100%=66.7%
(d) Esterification is a reversible reaction that reaches equilibrium. Not all reactants are converted to products. Additionally:
Some product may be lost during purification (e.g., during separation from the reaction mixture).
Some reactants may undergo side reactions.
The equilibrium position may not lie far enough towards the products.
Forgetting to account for all elements when determining empirical formula: Don’t assume a compound contains only C and H. Calculate the mass of each element present, then find oxygen (or other elements) by difference from the total sample mass.
Confusing molar concentration with mass concentration: mol/dm³ is moles per litre; g/dm³ is grams per litre. To convert between them, multiply by the molar mass. Don’t mix up the units in calculations.
Not adjusting for dilution or aliquot factors in titrations: If you dissolve a sample in 250 cm³ but only titrate 25 cm³, multiply your result by 10 to get the total amount in the original sample. Forgetting this factor gives answers that are 10x too low.