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Thermochemistry

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Exothermic r n:

T is positive  an increase in temp.   H is  0

Endothermic r n:

T is negative  a drop in temp.   H is  0



T have same value whether in oC or in Kelvin so if

T = 13.0 oC it will be also 13.0 K . Be careful !

 In calculations it is assumed that the density of all solutions is the same as the
density of water 1.0 g/cm3

 Heat gained (or lost) by calorimeter Q calorimeter is usually neglected.

E =  mtotal  C  T
 Solids are not included in the total mass because solids have very low heat capacities
compared to that of the solution.

Measuring enthalpy change of reaction in solution

"Calorimetry"
We assume that ALL the heat energy released in a chemical reaction is absorbed by
the contents of the calorimeter Thus

Qr×n =  ( Qsoln. + Qcalorimeter + ….)

Note: Since polystyrene cup is an insulator its heat capacity can be neglected & you
can assume that no energy is exchanged between the system & the surroundings.

Reasons of Using polystyrene cup (or plastic) :

o It is a good insulator so it conducts heat LESS well than metals

o has a very low specific heat capacity so it absorbs little heat
o It is inert whereas metal container might react with chemicals.

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1. Neutralisation reactions :
These reactions are exothermic in solution

H+ (aq) + OH (aq) 

 H2O (liq)
Quantity of heat = mass of solution  specific heat capacity  change in temp.
= ( Vacid + Vbase)  s.h.c  T
= ( macid + mbase)  C mixture  T
Where T = Tfinal  Tinitial

Example

In a simple calorimeter, by using a plastic cup inside an insulated box,

50.0 cm3 of 2.10 mol.dm–3 HCl were added to 50.0 cm3 of 2.00 mol.dm–3
NaOH and the temperature changes by 13.0 oC.
Assume that the specific heat capacity of this weak solution is the same as water
Csolution = 4.2 kJ kg –1 K–1 and the density of each solution = 1.0 g/cm3
Also, assume that all the heat from the reaction heats the water, raising the
temperature from T1 to T2.
Answer
Both solutions have a density of 1.0 g/cm3
The mass of 50.0 cm3 of HCl is = 50 g or 0.05 kg,
 heat produced = ( macid + mbase)  C mixture  T
Q = (0.05 + 0.05) kg  4.2 kJ kg–1 K–1  (13.0 K)
= 5.46 kJ
HCl + NaOH 
 NaCl + H2O
1 mol 1 mol
0.105 mol 0.1 mol Note
The heat absorbed by the
calorimeter Qcalorimeter
Limiting ( plastic coffee cup) was
Q  5.46 neglected & not included
 H =  =   54.6 kJ.mol 1 in the calculation!
n lim iting 0.1 mol
[Negative as heat is given out]

Remember to use the total volume of the mixture 100 cm3  100g
A common mistake is to use 50 cm3 !

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Improvements to the Procedure

 Add portions (e.g 2 cm3) of aqueous sodium hydroxide to the acid from a
burette.

 Read & record the temperature of the solution after each addition.

 From the graph, you can read off the maximum temperature rise, T,and
the volume of aqueous acid or (sodium hydroxide) added at neutralisation,
Vneut.draw two intersecting straight lines of best fit.

The lines cross represents the neutralisation of the acid by the sodium hydroxide
solution.

 Wait before reading temperature/ take a series of (temperature) readings

 Stir quickly after each addition &
 leave the thermometer in solution throughout or
 do not rinse the thermometer

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2. Displacement reactions
A metal that is more reactive than another will displace a less reactive one
from compound or solution.
Zn(s) + CuSO4(aq)   ZnSO4(aq) + Cu(s)
blue colourless brown
Fe(s) + 2Ag+(aq) 
 Fe2+(aq) + 2Ag(s)

Example 5.0 g of zinc powder was added to 50.0 cm3 of 1.0 mol dm–3 aqueous copper(II)
sulfate in a polystyrene cup. The temp. rose by 45.0 oC
C solution = 4.2 J g1 K1
Calculate the enthalpy change for this reaction in kJ mol –1.
Answer
Assuming density of solution is 1.0 g/cm3 Then the mass of 50.0 cm3 is
Explain why the mass of therefore equal to 50 g or 0.05 kg,
zinc is not used in the  Energy transferred =  msoln  C  T
calculation of the heat Q =  50 g  4.2 J g1 K1  45.0 K
energy for the reaction. =  9450 J
Ans: =  9.450 KJ
The heat capacity of 50
nCuSO4  [CuSO 4 ]  V = 1.0 mol dm3  dm 3 = 0.050 mol
zinc is negligible. 1000
OR m 5
zinc absorbs less heat n Zn    0.076 mol
M r 65.4
than solution

Zn(s) + Cu2+(aq)  Zn2+(aq)

 + Cu(s)
1 mol 1 mol
0.076 mol 0.050 mol

Limiting
Q  9.450
 H =  =   189 kJ.mol 1
n lim iting 0.05 mol
= – 190 kJ mol–1
[negative as heat is given out]

0.85 g of anhydrous LiCl (Mr = 42.4 g mol1) is added to 36.0g of water.

The temp. rises from 25.0oC to 30.0 oC. Calculate the enthalpy change of
solution of one mole of LiCl. Use C solution = 4.2 J g1 K1
Ans : H = –38 kJ mol–1

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Improvements to the Procedure

Improvement Insulate the apparatus by using a calorimeter which consists of
two polystyrene coffee cups and a plastic cover (lid).

Reason Insulation minimizes / reduces heat loss to the surrounding

air or absorbs less heat

Improvement Use a pipette or a burette instead of measuring cylinder

Reason More accurate volume (than measuring cylinder)

Improvement Measure temperature for several minutes before the addition

Reason Allows more accurate value for the initial temperature.

Improvement Stir the mixture quickly.

Reason This ensures even temperature / This ensures a complete

and faster reaction so less heat loss with time.

Improvement Use finely divided iron or smaller pieces

Reason Reaction is faster so less heat loss with time

o Carry out another experiment to find the calorimeter

constant and use it in calculations.

Improvement Measure the temperature more often

Reason Allows for better extrapolation to obtain a more

accurate value of maximum temperature change from graph

o Take a series of temp. readings over a period of time intervals rather than simply
initial and final readings.

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Temperature Extrapolation Method

HOW? Draw best straight lines through my data and extrapolate back those
lines to the time of mixing in order to find a more accurate maximum
temperature change T from graph.

 Reason 1 Any fluctuations in temperature can be smoothed out or to

minimise reading error.

 Reason 2 Able to allow for cooling effect / able to calculate more accurate
temperature change
This will separate the temp. change due to the reaction from the
temp. change due to heat entering or escaping the calorimeter from
the outside.
The temperature slowly
 
declines as heat energy is
given out to the surroundings.


T corrected 

   

1 2 3 3½ 4 5 6

Time /min

50 cm3 of a 1.00 mol dm–3 solution of potassium carbonate K 2CO3(aq)was

added to 50 cm3 of a 1.00 mol dm–3 solution of calcium chloride, CaCl2(aq).
The temperature fell by 1.5 °C.
You may assume that
 1.0 cm3 of solution has a mass of 1.0 g.
 The specific heat capacity of the solution is 4.2 J g–1°C–1.
Calculate the enthalpy change for the reaction, giving your answer to two
Measurement
significant figures. of enthalpies of combustion

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Measurement of enthalpies of combustion

Energy change = mass of  specific heat capacity  temperature change
in joules solution of solution
/g / J oC –1 g –1 / oC

Measurements & Calculations

Mass (or volume) of water e.g 200g
Mass of burner + fuel ( before burning ) m1 = 198.46 g
water
water
Mass of burner + remaining fuel (after burning) m2 = 198 g

 mass of fuel burnt = m1 - m2

Spirit burner = 198.46 g  198g
++
spirit lamp
ethanol
Fuel = 0.46 g
 moles (amount) of C2H5OH burnt
m1 - m 2
n ethanol =
Mr
Assumptions 0.46 g
=
 No heat is absorbed by the (glass or 46 g mol 1
food can)calorimeter. = 0.01 mol
 There is no heat lost by radiation or
from the surface of water.
Initial temp. of water (before burning the fuel) T1 = 18.5 oC
 All the energy released by burning
the fuel(ethanol is transferred to the Final temp. of water (after burning the fuel) T2 = 28.5 oC
water.  rise in temp. T = T2 – T1
 The fuel(ethanol) undergoes = 28.5 – 18.5
complete combustion = 10.0 C  0
o

 The fuel is mainly pure ethanol. Qcalorimeter is neglected so the Heat gained by water is
Q gained = m water  C water  (T2 – T1 )
=  200g  4.18 J g –1 oC–1  10.0 o C
Qreaction= (Qsoln + Qcalorimeter) =  8360 J
= – 8.360 KJ
So 0.01 mol  8.360 KJ
1 mol ?
Hcomb C2H5OH =  836 kJmol –1

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Sources of errors in this experiment:

1. Loss in mass of the alcohol after weighing or during transfer by evaporation
since it is very volatile.

2. Loss of heat to the surrounding air from the top and sides of the calorimeter.
3. Incomplete combustion of the alcohol [due to insufficient oxygen
so the reaction does not go to completion thus there will be black carbon or
soot]
 Incomplete combustion makes Hcomb less exothermic (lower) than that in
Data book!

4. The heat capacity of the apparatus is not included

or is not small to be neglected / some heat is absorbed by the calorimeter.

Improvement of the Results/Data

1. Transfer the weighed amount of alcohol as quick as possible to minimize

evaporation(Since alcohols are volatile)

2. Measuring the mass of water using a burette.

3. Insulate the sides of the beaker (calorimeter) using a mineral wool or a lid
and providing a draught screen or use a lid to reduce the loss of heat

4. Carry out a different experiment to calculate the heat capacity of the whole
apparatus. Calibrating the calorimeter(apparatus) which allows for errors
due to heat loss.

Note

Using a digital thermometer would not improve the accuracy of the result because . .
...
the error in reading temperature is less than the effect of ignoring significant
heat loss to surrounding air or absorbed by the calorimeter!!

 Solved exercises
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1. (a) If Hocomb. = 725 kJ mol-1 for CH3OH(l) then write a thermochemical

equation for the complete combustion of liquid methanol.

CH3OH(l) + 1½O2(g) 
 CO2(g) + 2H2O(l) Hocomb.= 725 kJ mol1

(b) Calculate the heat liberated on burning 6.4 g of CH3OH(l)

m 6.4
nCH 3OH    0.2mol
Mr 32

1 mol of methanol  725 kJ

0.2 mol ?

 Amount of heat = 0.2  (725) = 145 KJ

2. 1.0 g of methanol (CH3OH) produces 22.65 KJ of energy when completely burnt in

excess oxygen. Calculate the molar enthalpy of combustion of methanol.

m 1.0 g
n   0.03125mol
M r 32 gmol 1

0.03125 mol  22.65 KJ

1 mol Hocomb = ?

1 (22.65)
Hocomb =  725KJ  mol 1
0.03125

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Question 1
The apparatus shown in the diagram below may be used to find the enthalpy of
combustion of alcohols.

water

spirit lamp +
ethanol

Using the apparatus, a student recorded the results included in the table below.

Molar Mass ethanol, C2H5OH = 46.0 g mol–1

Volume of water in beaker = 200 cm3
mass of water in beaker = 200 g

Weighings
Spirit lamp + ethanol before combustion = 198.76 g
Spirit lamp + ethanol after combustion = 197.68 g

Temperatures
Water before heating = 19.5 oC
Water after heating = 38.1 oC
Specific heat capacity of water = 4.18 J g–1 oC–1

(a) What assumption is the student making about water to be able to state that its
mass is numerically equal to its volume?
(1)

(b) Calculate the heat gained by the water. Give your answer in kJ. (2)

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(c) Calculate the amount (number of moles) of ethanol used. (2)

(d) Using your values from (b) and (c), calculate the enthalpy of combustion of
ethanol. Give your answer to a number of significant figures consistent
with the readings in the table. Include a sign and units in your answer.

(3)
(e) The student’s evaluation of the experiment is given below.

My calculated value of the enthalpy of combustion was numerically much less than
the data book value. The reasons for my low value include:

1 heat losses to the surrounding air;

2 when I re-checked the mass of the spirit lamp and ethanol after combustion, I
noticed that it had lost mass even when it was not being used;
A black solid which formed on the base of the beaker.

(i) Explain why the spirit lamp and ethanol lost mass even when not in use.
(1)

(ii) Suggest the identity of the black solid. Explain why its formation will

lead to a low value for the enthalpy of combustion.

Identity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Explanation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)

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Question 2
In an experiment to find the enthalpy change when copper is displaced from a
solution of copper ions excess zinc was added to 50.0 cm3 of 1.00 mol dm–3
aqueous copper(ii) sulfate in a plastic cup.

Zn(s) + Cu2+(aq) 
 Zn2+ (aq) + Cu(s)

The temperature of the solution in the cup was measured every minute for 10 minutes
with the zinc being added after 3.5 minutes. The temperature readings are shown on the
graph below.
70
Temperature/°C

×
60 ×
×
×
×
×
50 ×

40

30

20 × × ×

10
0 1 2 3 4 5 6 7 8 9 10
Time/minutes

(a) Suggest two reasons why a series of temperature readings is taken rather
than simply initial and final readings.

First reason. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Second reason. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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(b) Use the graph to calculate the maximum temperature change, T, as the
reaction takes place.

      T = ...........................................°C

(c) Calculate the enthalpy change for the reaction ,giving your answer to an
appropriate number of significant figures.

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Question 2
A student carried out an experiment to find the concentration of a solution of nitric acid
and also its enthalpy of neutralisation.
• The solutions of nitric acid and sodium hydroxide were allowed to reach the same
temperature.
• 50.0cm3 of the nitric acid was pipetted into a polystyrene cup.
• A burette was filled with a solution of 2.0 mol dm–3 sodium hydroxide, NaOH.
• The initial temperature of the acid was recorded.
• The sodium hydroxide was added to the acid in 5.0 cm3 portions.
• After each addition, the mixture was stirred and the maximum temperature
recorded.
• This was repeated until 45 cm3 of the sodium hydroxide solution had been added.

The student plotted the results, as shown below.

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(a) Complete the graph by drawing two intersecting straight lines of best fit.

(b) The point where the lines cross represents the neutralisation of the nitric acid by
the sodium hydroxide solution.

Use the graph to find:

(i) the volume of 2.0 mol dm–3 sodium hydroxide solution, NaOH, that reacts
exactly with the 50 cm3 of the nitric acid. (1)

(ii) the maximum temperature change, T, in the reaction.

T = ...........................................°C

(c) The information in (b)(i) and the equation below can be used to calculate the
concentration of the nitric acid.

NaOH(aq) + HNO3(aq) 
 NaNO3(aq) + H2O(l)

(i) Calculate the amount (moles) of sodium hydroxide used to neutralise the 50 cm3
of nitric acid. (1)

(ii) Write the amount (moles) of nitric acid in 50.0 cm3 of the solution.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (1)

(iii) Hence calculate the concentration of nitric acid, HNO3, in mol dm–3. (2)

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(d) (i) Use the data from (b) to calculate the heat change for this reaction.

The density of the mixture produced at neutralisation is 1.0 g cm–3 and the
specific heat capacity of the mixture is 4.2 J g–1°C–1.

Heat change = mass × specific heat capacity × ΔT (2)

(ii) Use your answer from (d)(i) and (c)(iii) to calculate the enthalpy of neutralisation
per mole of nitric acid, HNO3. Include a sign and units with your answer. (3)

(e) The enthalpy of neutralisation found by this method may be less exothermic than
the data book value because of heat loss.

Suggest ONE way to reduce the error due to heat loss. (1)

LAS Chemistry Practicals (3B) 2012 - 2013 Tarek.A. Aoudi