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HEAT OF NEUTRALISATION

Aims
1. To determine the heat capacity C, of the calorimeter
2. To determine the heat of neutralisation of a strong acid/strong base reaction (HCl/NaOH)
3. To determine the heat of neutralisation of a weak acid/strong base reaction (CH 3COOH/NaOH)
4. To determine the H of ionisation of CH3COOH using data obtained from experiment
5. To compare values obtained/derived from experimental results with literature values

Results & Discussion


Part 1- Determining the heat capacity C, of the calorimeter

Mass of Calorimeter with magnetic stirring bar & thermometer/g


Mass of Calorimeter with magnetic stirring bar & thermometer +
200ml of deionized water/g
Mass of 200 ml of deionized water/g

262.07
465.43
203.36

Table 1.1: Calculated mass of 200g of ionised water

Time/s

12

15

18

21

24

27

30

40

Temperature/C

24.8

24.8

24.8

24.8

24.8

24.8

24.8

24.8

24.8

24.8

24.8

Time/s

60

70

80

90

100

110

120

130

140

150

160

Temperature/C

24.8

24.8

24.8

24.8

24.8

24.8

24.8

24.8

24.8

24.8

24.8

Time/s

180

210

240

270

300

Temperature/C

24.8

24.8

24.8

24.8

24.8

Table 1.2: Temperature of the 200 ml of deionised water at specific intervals

Time/s

12

15

18

21

24

27

30

40

Temperature/C

26.3

28.0

28.0

28.1

28.1

28.1

28.1

28.1

28.1

28.0

28.0

Time/s

60

70

80

90

100

110

120

130

140

150

160

Temperature/C

27.8

27.8

27.7

27.7

27.7

27.7

27.7

27.7

27.7

27.6

27.6

Time/s

180

210

240

270

300

Temperature/C

27.6

27.6

27.5

27.5

27.5

Table 1.3: Temperature of the solution after addition of 2.2 ml of conc H2SO4 to the 200 mil of deionised water
at specific time intervals

Tf =28.1oC
Graph of Tempe rature against Time of Dilution of conce ntrate d H2SO4
30

T0 =24.8oC

28

Temperature/C
26

24

50

100 150 200 250 300 350 400 450 500 550 600 650

Time/s

Figure 1.1: Graph of Temperature against Time of Dilution of concentrated H2SO4


Table 1.4: Titration results
1st Titration

2nd Titration

3rd Titration

18.10

18.10

18.00

Values used

Average Vol of NaOH used/cm3

18.05

Vol of NaOH used/cm3

H2SO4 (aq) + 2NaOH (aq) Na2SO4 (aq) + 2H2O (l)


No. of moles of NaOH reacted = 0.01805 L*0.5263 M = 0.009499715 mol

No. of moles of H2S04 reacted =

No . of moles of NaOH reacted


2

0.009499715
2

= 0.0047498575 mol
Since 25mL of solution from calorimeter is titrated with the NaOH,
Concentration of H2S04 in calorimeter = 0.0047498575 mol/0.025 L =
0.1899943 molL-1
No. of moles of H2SO4 in calorimeter = 0.1899943 molL -1*0.2022 L = 0.0384168
mol

From Table
1

Molarity of H2SO4 in 202.2 mL of solution = 0.0384168 mol/

(203.36 x 10-3 kg)

= 0.18891 mol/kg

Heat liberated during dilution of the concentrated acid = -H dWx (Joules)


Where W =

mass of water in kg

x =

molality of the acid produced by the dilution

Hd =

enthalpy of dilution = -75.58 x 103 J/mol

The heat liberated by the dilution process raised the temperature of the acid and the
calorimeter from T1 to T2.

- HdWx = [(4.184 x 103)W + w][Tf T0] ----- Equation 1


Where w = heat capacity of calorimeter in J/K
Rearranging Equation 1: w = (-HdWx) / (Tf T0) (4.184 x 103)W
3

w=

(75.58 x 10 J / mol)(203.36 x 10 kg )(0.18891mol / kg)


28.124.8

- (4.184 x 103)(203.36 x 10-3

kg)
= 29.0 J/K

Part 2- Determining the heat of neutralisation of a strong acid/strong base reaction (HCl/NaOH)
Temperature (C)
24.2
23.7

Thermometer #1
Thermometer #2

Calibration
-0.5C
Not required

Table 2.1: Temperatures measured by two thermometers in a beaker of water

Time/s

60

120

180

240

300

Temperature of HCl/C

23.7

23.7

23.7

23.7

23.7

Temperature of NaOH/C

23.7

23.7

23.7

23.7

23.7

Table 2.2: Temperature of HCL & NaOh before mixing

Time/s

12

15

18

21

24

27

30

40

Temperature/C

27.1

27.4

27.5

27.5

27.6

27.6

27.6

27.6

27.6

27.6

27.6

Time/s

60

70

80

90

100

110

120

130

140

150

160

Temperature/C

27.5

27.5

27.5

27.5

27.5

27.5

27.4

27.4

27.4

27.4

27.4

Time/s

180

210

240

270

300

Temperature/C

27.4

27.4

27.4

27.4

27.3

Table 2.3: Temperature of mixed solution (HCl + NaOH)

Gra ph f o r n e u t ra l i s a t i o n o f h cl & n a o h
28
27.5
27

T =27.6oC

26.5
26

25.5
Temperature/C
Mixture THCl = 23.7C
Linear (Mixture)

NaOH

HCl

Mixture

25

TNsOH = 23.7C
24.5

24
23.5
23

50 100 150 200 250 300 350 400 450 500 550 600 650

time/s

Figure 2: Graph of Temperature against Time for Neutralization of HCl and NaOH

HCl (aq) + NaOH (aq) NaCl (aq) + H2O (l)


Concentration of HCl used = 0.5236 M

Volume of HCl used = 0.100 L

Concentration of NaOH used = 0.5263 M

Volume of NaOH required = 0.0995 L

Mass of acid and flask/g

209.35

Data values for

Mass of empty flask/g

109.50

calculation of Hneut of
HCL
0.09985

Mass of acid used/g


99.85
(macid )|Hneut| =
Mass of HCL/kg (WHCl)
Mass of calorimeter with
T1)+(4.184 x
292.76
NaOH/g
Mass of NaOH/kg (WNaOH)
w(T T2)
Mass of dry calorimeter/g
191.45
Temp of NaOH/C (T1)
No of of
moles
of HCl
Mass
NaOH
used/g
101.31

(4.184 x 103)WHCl(T
103)WNaOH(T T2)+

0.1013

(Equation 2)

23.7

Concentration of HCl

Temp of HCl/C (T2)

23.7

used

Final Temp of mixture/C (T)

27.6

neutralised, macid =
used x Volume of HCl

= (0.5236 M)(0.100 L)
= 0.05236 mol
|Hneut| =

( 4.184 x 10 3 ) ( 0.09985 kg ) [( 27 .623.7 ) C ] + ( 4.184 x 103 ) ( 0.1013 kg ) [ ( 27.623.7 ) C ] + ( 29.0 J /K ) [ ( 27.623.


0.05236 mol
= 64847 J/mol
Hence, Hneut = -64.8 KJ/mol

Part III Determining the heat of neutralisation of of a weak acid/strong base reaction
(CH3COOH/NaOH)
Temperature (C)
24.4
23.8

Thermometer #1 (used for flask with acid)


Thermometer #2 (used for calorimeter with base)

Calibration
-0.6C
Not required

Table 3.1: Temperatures measured by two thermometers in a beaker of water

Time/s

60

120

180

240

300

Temperature of CH3COOH/C

23.7

23.7

23.7

23.7

23.6

Temperature of NaOH/C

23.8

23.8

23.8

23.8

23.8

Table 3.2: Temperature of CH3COOH & NaOH before mixing

Time/s
Temperature/C

12

15

18

21

24

27

30

40

25.5

27.1

27.4

27.5

27.5

27.5

27.5

27.5

27.5

27.5

27.5

Time/s

60

70

80

90

100

110

120

130

140

150

160

Temperature/C

27.5

27.5

27.5

27.5

27.5

27.4

27.4

27.4

27.4

27.4

27.4

Time/s

180

210

240

270

300

Temperature/C

27.4

27.4

27.4

27.4

27.3

Table 3.3: Temperature of mixed solution (CH3COOH + NaOH)

Graph for Ne utralisation of CH3COOH & NaOH


27.55
27.5
CH3COOH 27.45

NaOH

CH3COOH

Linear (CH3COOH)

27.4

Temperature/C

27.35
27.3

NaOH

27.25
27.2
250

300

350

400

450

500

550

600

650

Time/s

Figure 3.1: Graph of Temperature against Time for Neutralization of CH3COOH and NaOH

CH3COOH (aq) + NaOH (aq) CH3COO-Na+ (aq) + H2O (l)


Concentration of CH3COOH used = 0.5263 M

Volume of CH3COOH used = 0.100 L

Concentration of NaOH used = 0.5263 M


Volume of NaOH required = 0.100 L
Data values for calculation of Hneut of CH3COOH
Mass of acid and flask/g
209.20
Mass of CH3COOH/kg (W1)
0.09933
Mass of empty flask/g
109.37
0.09983
Mass of acid used/g Mass of NaOH/kg
99.83(W2)
Temp of NaOH/C
Mass of calorimeter with
291.31(T2)

23.8

NaOH/g
Temp of CH3COOH/C (T1)
Mass of dry calorimeter/g
191.48

23.6

Mass of NaOH used/gFinal Temp of99.83


mixture/C (T)

27.5

(macid )|Hneut| = (4.184 x 103)W1(TT1)+(4.184 x 103)W2(T T2)+ w(T T2)

(Equation 2)

No of moles of CH3COOH neutralised, macid = Conc of CH3COOH used x Vol of CH3COOH used
= (0.5263 M)(0.100 L)
= 0.05263 mol
|Hneut| =

( 4.184 x 10 3 ) ( 0.09983 kg ) [( 27.523.6 ) C ] + ( 4.184 x 103 ) ( 0.09983 kg ) [ ( 27.523.8 ) C ]+ ( 29.0 J / K ) [ ( 27.523


0.05263 mol
= 62200 J/mol
Hence, Hneut = -62.2 KJ/mol

Part IV - To determine the H of ionisation of CH 3COOH using data obtained from experiment

By Hess Law,
Hionization (CH3COOH) = Hneut (CH3COOH) Hneut (HCl)
= -62.200 KJ/mol (-64.847 KJ/mol)
= +2.647 KJ/mol

Part V - To compare heat of neutralisation values derived from experimental results with
literature values

HCl & NaOH


CH3COOH & NaOH

Experimental Hneut/kJmol-1

Literature Hneut/kJmol-1

-64.8
-62.2

-57.32
-55.42

Table 5.1: Literature values and experimental values of heats of neutralisation

Data analysis
As seen from Table 5.1, the data obtained from the experiment is mediocre considering that the %
deviation for the both heat of neutralisation of was more than 10%. To have deviations from the

% Deviation
13.09%
12.27%

literature values is expected as well since the experimental conditions are somewhat different and this
being a temperature related experiment, the obtained readings are bound to vary along with variation
of ambient temperature. However, similar to the experiment conducted, the experiment that yield the
literature values is conducted in a professional lab setting and logically speaking, there should only be
subtle differences in the results, yet the order of magnitude of deviation is one. Thus, it is ostensible
that there are some inherent and procedure flaws that should be looked at. That being said, it was
positive that the heat of neutralisation for the weak acid-strong base reaction was less exothermic than
that of the strong acid-strong base as this was being expected (will be covered more extensively in the
conclusion section). Evidently the plot curve for both reactions are rather close to their respective
extrapolation lines, which is representative of what the temperature of the solutions would have been
like if there were no heat loss, thereby suggesting that heat loss was minimal throughout the procedure
and results were pretty accurate. However, precision was slightly lacking during the final stages of
both reactions as the steady temperature of the neutralised solution fluctuates slightly by 0.1C

The deviations from the literature values could have arose due to the following reasons:
1. Random/Systematic errors
There could be existing systematic errors present in the laboratory thermometers and the mass
balances. The laboratory thermometers could have registered a degree higher or lower for
some of the measurements and the balances may be defective and indicate a mass higher or
lower than the actual values. All of these systematic errors could have affected measurement
values such as mass readings (W, W1 & W2) and temperature readings (T0, Tf, T1 & T2) which
in turn introduce uncertainties to calculated values such as the heat capacity of calorimeter
and the heats of neutralisation.
There could be occurrences of human error as well. This could arise firstly due to a significant
time lag between the last measured temperature of the 200ml of deionized water (at the 300s
mark) and the addition of concentrated sulphuric acid which results in further loss of heat to
surrounding via radiation during that time frame, thus rendering a lowered starting
temperature after dilution with the conc H 2SO4. Also, there were instances where the metal tip
of the laboratory thermometer was accidentally touched which could cause a transfer of heat
from the hand onto the thermometer, thus artificially raising the temperature reading. Finally,
parallax error may occur as well, especially while trying to read the initial and final burette
reading (i.e. not reading the meniscus at eye level). Lastly,
2. Non-standard conditions/apparatus
The settings and apparatuses of the experiments conducted which yield the literature values
and that for the experimental values are likely to be different and culminated in the deviations
observed. For example, the heat capacity of the calorimeter used for the literature values

could have a higher heat capacity which explains why the magnitude of the heat of
neutralisation value for both instances is higher. Also, the ambient temperature of the
laboratory for the literature values could possibly be higher, which led to less heat loss to
surrounding and thus more exothermic heats of neutralisation.
3. Unequal total volume of reagents
It is noteworthy that for the titration between H2SO4 & NaOH, the total volume of the mixture
is vastly smaller from that of the subsequent neutralisation reactions. This represent a source
of unequal heat loss as the area of exposure with the inner wall of the calorimeter would differ
with the HCl/NaOH & CH3COOH/NaOH having greater thermal contact with the calorimeter.
As such the heat capacity of calorimeter (w) attained in part (i) should not apply to the
neutralisation reactions in part (ii) & part(iii). This is so since heat capacity = specific heat
capacity x mass, with greater mass of the calorimeter in contact with the reagents, the heat
capacity value of calorimeter would be greater.
4. Limitation of apparatuses
Calorimeter
The calculated value for the heat capacity of the calorimeter may be inaccurate and some way
off the true value due to limitations of its design. Throughout the procedure, there were
openings for further heat loss as there is a hole in the cover of the calorimeter and the solution
was exposed to the surrounding when the cover was removed to pour in the conc H 2SO4
Laboratory thermometer
The laboratory thermometer is only able to measure the temperature of a localised region
surrounding its tip. As such, the temperature at the spot being measured may not be the same
elsewhere in the solution. Furthermore, the laboratory thermometer is unable to record small
changes in temperature as its precision is only up to 0.1C. With such a precision, the
uncertainty is higher as well which can be amplified further during the calculations. Finally,
since such acid-base reaction occurs at a highly rapid rate and with laboratory thermometers
not being the most sensitive apparatus around, the thermometer readings may not correlate to
the time it was recorded as per the stopwatch due to any plausible delays between the
temperature at the exact time and at the time the reading was registered. This led to greater
inaccuracy.
Suggestions for improvements
1. A data logger could have been used in place of laboratory thermometers. Being much more
sensitive than thermometers, it could provide highly accurate temperature readings at that exact
moment in time and with frequency of it tuned to the desired time intervals. This could eliminate
human errors during the recording process and systematic errors inherent within the laboratory
thermometer. In addition, temperature could be measured at smaller time intervals, thus resulting

in a larger amount of readings which reduce the uncertainty level when the data values are used
for calculation and also a more exact depiction of the temperature-time graphs.
2. A better simulation of the experimental conditions used in the experiment that yield the literature
values could have been the case. The literature values of the heat of neutralization are for standard
conditions of 298K, 1 atm and 1mol/L. While it may be difficult to re-enact the entire experiment
with the same standard conditions, certain aspects can be mitigated with a few measures in place.
Firstly, the reagents could all have been with concentration of 1 mol/L. Secondly, prior to the
actual titration, the experiment set up could have been placed in water bath with temperature of
298K to maintain standard temperature as far as possible. It is important to take note that the aircondition temperature should not be set too low as well and on a hot day, it might be wise to turn
down the temperature to attain room temperature as far as possible.
3. The design of the calorimeter could have been further improved. As mentioned in the previous
section, there were a few flaws in design which contributed to greater heat loss. Firstly, a
lever/cap could have been introduced to the cover of the calorimeter which can be open/close with
ease. As such, while pouring the acid into the calorimeter, it could be done so without opening the
screw-on cover and through the opening beneath the lever/cap. Thereafter, the lever/cap can be
swiftly attached back and this reduce exposure time the mixture have with the surrounding. In
addition, an inert insulating material could have been placed inside the calorimeter to minimise
heat conducted away by the calorimeter.
Conclusion
The aims of this experiment as stipulated in the opening section has been explored and achieved by
conducting the experiment and evaluating the subsequent results. The experimentally determined heat
of neutralisation of the HCl & NaOH reaction (-64.8 KJ/mol) and CH 3COOH & NaOH reaction (62.2 KJ/mol) are both exothermic which is aligned with theoretical deduction of an energetically
feasible reaction since heat released from the breaking of chemical bonds within the product
molecules must be sufficiently high enough to break the chemical bonds within the reactant molecules
in order for the reaction to occur. In addition, it is observed that the heat of neutralisation of the latter
neutralisation reaction is less exothermic than the case of the former. The difference between the two
values (+2.647 KJ/mol) is known as the heat of ionisation. Neutralisation is a chemical reaction in
which an acid and base react to form salt. In this case, the acids (CH 3COOH & HCl) and base (NaOH)
are Arrhenius acids and base which produce water during the reaction. 3 However, CH3COOH is a
weak acid that only partially dissociate in water to produce hydronium ions (H 3O+) and thus some of
the heat evolved during the reaction is absorbed to further dissociate CH 3COOH to form more H3O+
ions that are required to react with the OH - ions produced by NaOH to form water. On the other hand,

HCl is a strong acid that completely dissociate in water to produce H 3O+ ions and as such, the heat of
neutralisation would be more exothermic.

References
1. Department of Chemistry, NUS (2013). CM1502 General and Physical Chemistry for
2.

Engineers Practical Booklet. (accessed on Mar 10, 2014)


A. S. Negi, S. C. Anand, 2004. A textbook of physical chemistry. pp 221.
http://books.google.com.sg/books?
id=wyP_V3X8YOIC&q=page+221#v=onepage&q=page%20221&f=false (accessed on

Mar 10, 2014)


3. Wikipedia. http://en.wikipedia.org/wiki/Neutralization_(chemistry) (accessed on Mar 10,
2014).