Purpose

To investigate the heat of ionization of a weak acid. When acids and bases are combined
a neutralization reaction to occurs which produces salt, and water and the evolution of heat. In
order to measure the quantity of heat produced, a thermally insulated container known as a
calorimeter is used. This experiment utilized a Styrofoam calorimeter to isolate and measure this
heat formed by reactions involving two different acids: the strong acid hydrochloric acid [1], and
the weak acid dichloroacetic acid [2], when mixed with the strong base sodium hydroxide.
HCl + NaOH NaCl + H2O
Cl2CH2COOH + NaOH Cl2CH2COONa + H2O

[1]
[2]

However since the Styrofoam cup is a decent insulator and not perfect some of the heat
will be absorbed by calorimeter itself. In order to account for this the heat capacity of the
calorimeter is determined by measuring the temperature change when a known amount of warm
water and cold water is added to the calorimeter. The amount of heat lost to calorimeter is the
difference between the heat lost by the warm water and that gained by the cool water.
The temperature data from this reaction will be used to calculate the heat produced for
each mole of the acid used, also known as the molar heat of neutralization, allowing for a
comparison to be made between these two different acids. This information will allow for
determination of what has a greater heat of neutralization: the reaction between a strong acid and
a strong base, or a weak acid and a strong base.
Method
Part 1: Heat Capacity of Calorimeter
A graduated cylinder was used to obtain 50 mL of distilled water. This water was then
transferred to the Styrofoam cup calorimeter, which was mounted to a stir plate using a stand and
clamp. A stirring rod was put into the cup and a digital thermometer (Calibrated to +/-0.1C)
was used to find the temperature of the water. 50 mL of warm water in a graduated cylinder, was
obtained from a warm water bath. This warm water was added immediately to the Styrofoam cup

calorimeter and a stopwatch was initiated once all the water had been added. The temperature
was noted at 15 second intervals until 4 minutes was reached.
Part 2: The heats of neutralization
A graduated cylinder was used to measure out 50 mL of NaOH, which was transferred to
the Styrofoam cup calorimeter. A stirring rod was added to the cup and a digital thermometer was
used to record the temperature. A graduated cylinder was used to measure out 50 mL of HCl,
which was allowed to stand until at room temperature. The temperature was then recorded using
a digital thermometer. The HCl was then quickly added and a stopwatch was initiated when the
first drop was added. The temperature was recorded at 15 second intervals until 4 minutes was
reached. Part 2 was repeated, except HCl was substituted with dichloroacetic acid.
Results
32.3
32.2

f(x) = - 0x + 32.19
R = 0.55

32.1
32
Temperature of mixture (C) 31.9
31.8
31.7
31.6

15
0

45
30

75
60

105 135 165 195 225

90 120 150 180 210 240

Time after mixing (s)

Figure 1: Graph of the temperature versus time data for addition of hot water and cold water in
the calorimeter. This reaction is used to determine the heat capacity of the Styrofoam cup
calorimeter; the heat which is lost to the calorimeter.

30
f(x) = 0.01x + 28.01
R = 0.13

28
26
Temperature of mixture (C)

24
22
15
0

45
30

75
60

90

105 135 165 195 225

120 150 180 210 240

Time after mixing (s)

Figure 2: Graph of the temperature versus time data for the reaction between the strong acid
hydrochloric acid (HCl) and strong base sodium hydroxide (NaOH).
30
28
26
24
Temperature of mixture (C)
22
20

f(x) = 0.01x + 27.16

R = 0.12

15
0

45
30

75
60

90

105 135 165 195 225

120 150 180 210 240

Time after mixing (s)

Figure 3: Graph of the temperature versus time data for the reaction between the weak acid
dichloroacetic acid (DCA) and strong base sodium hydroxide (NaOH).
Table 1: The intial temperature, final temperature and change in temperature of the reactants in
each of three calorimeter reactions.
Initial
Final
Change in
Temperature, Temperature,
Temperature,
Ti
Tf
T
Addition of hot
Hot water
43.3 +/- 0.1C 32.19 +/- 0.1C -11.11+/- 0.1C
water to cold water
Cold water
22.0 +/- 0.1C
10.19 +/- 0.1C
Neutralization of
Hydrochloric acid 21.5 +/- 0.1C 28.01 +/- 0.1C
-6.51+/- 0.1C
strong acid-strong
(HCl)
base
Sodium hydroxide 22.8 +/- 0.1C
5.21 +/- 0.1C
(NaOH)
Neutralization of
Dichloracetic acid 21.4 +/- 0.1C 27.16 +/- 0.1C -5.76 +/- 0.1C
weak acid-strong
(Cl2CH2COOH)
base
Sodium hydroxide 21.8 +/- 0.1C
5.36 +/- 0.1C
(NaOH)

Heat capacity of calorimeter

Initial temperature of hot water is 43.3 C (316.30 K) and cold water is 22.0 C (495 K)
| heat lost by hot water | = | heat absorbed by cold water | + | heat absorbed by calorimeter |
Vh CpH2O T = Vc CpH2O T1 + Cpcal T1
E hot water = E cold water + E calorimeter
mcT = -(mcT + cT)
| (50.00 mL)(1.00g/mL)(4.18 J/g K)(-11.11)C | = -[ |(50.00mL)(4.18 J/g K)(1.00g/mL)(10.19) C | +
| Cpcal (10.19) C |]
2321.99 J = 2129.71 J + Cpcal (10.19)
Cpcal = 18.87 J/K
Therefore the Cp of the calorimeter is 18.87 J/K.

Neutralization of strong acid (HCl) and strong base (NaOH)

The instantaneous temperature from the reaction between hydrochloric acid and sodium
hydroxide is 28.01 C (301.01 K) which is also considered the final temperature.
- Initial temperature of hydrochloric acid is 21.50 C (294.5 K)
- Initial temperature of sodium hydroxide is 22.80 C (295.8 K)

= | (50mL)(1g/mL)(4.18J/g K)(6.51K)| + |(50mL)(1g/mL)(4.18J/g K)(5.21K) | + |(18.87J/K)(5.21K)|

= 2547.79 J

Therefore the total heat evolved from the acid-base neutralization is 2547.79 J.
The number of moles of acid in base neutralized
n = c*v
number of moles of HCl = (0.999 M)*(0.05L) = 0.0499 moles
number of moles NaOH = (0.907M)*(0.05L) = 0.0454 moles (limiting)
Neutralization of 1 mole of HCl:
2547.79 J * (1 mol/0.0454 mol) = 56118.72 J/mol = 56.12 kJ/mol
Since, NaOH is limiting the number of moles HCl is equal to number of moles of NaOH.
Therefore, the molar enthalpy of neutralization between NaOH and HCl is 56.12 kJ/mol.
*since the reaction is exothermic the value becomes negative (Release of heat energy)

Neutralization of weak acid (DCA) and a strong base (NaOH)

Number of moles of DCA = (1.007 M)(0.05 L) = 0.0504 moles
Number of moles of NaOH = (0.907M)*(0.05L) = 0.0454 moles (limiting)
H3O+(aq) + OH- 2H2O(l) - [reaction A]
CHCl2COOH + OH- + H2O(l) CHCl2COO- + 2H2O(l) - [reaction B]
- to determine amount of heat released it is necessary to know the number of moles of hydronium
neutralized
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
A-(aq) + H2O(l) HA(aq) + OHH2O(l) H3O+(aq) + OHSimultaneous equations:

Five major species: HA, A-, H3O+, OH-, Na+

1. Ka = [H3O+][A-] / [HA]
2. Kw = [H3O+][OH-] = 1*10-14
[OH] = kw / [H3O+]
3. [HA]+[A] = CA = 1.007 M
[HA] = CA [A-]
+
4. [Na ] = 0.907 M
5. [Na+] + [H3O+] = [OH-] + [A-]
[A-] = [Na+] + [H3O+] - [OH-]
= 0.907 + [H3O+] - kw / [H3O+]
Assume [H3O+] >>> [OH-]
= 0.907 + [H3O+] - kw / [H3O+]
Ka = [H3O+](0.907 + [H3O+]) / 1.007 - (0.907 + [H3O+])
Let [H3O+] = x

From literature Ka2 = 5.62 * 10-2

5.62 * 10-2 = x2 + 0.907x / 0.1 x
5.62 * 10-2 (0.1 x) = x2 + 0.907x
5.62 * 10-3 0.0562x = x2 + 0.907x
0 = x2 + 0.9632x 0.00562
Solve quadratic equation
a=1
b = 0.9632
c = -0.00562
x = 5.8 * 10-3
Therefore the [H3O+] is 0.0058
Number of moles of [H3O+] = (0.0058 M) * (0.05L) = 2.9 * 10 -4 mol
Therefore ther number of moles hydronium is 2.9 * 10 -4

= | (50mL)(1g/mL)(4.18J/g K)(5.78K)| + | (50mL)(1g/mL)(4.18J/g K)(5.36K)| + |18.87J/K)(5.36K)|

= 2429.4 J

Therefore the total heat evolved from neutralization is 2429.4 J.

Heat released by reaction B: CHCl2COOH + OH- + H2O(l) CHCl2COO- + 2H2O(l)

2429.4 J = (56118.72 J/mol )* (2.9 * 10-4 mol ) + | heat released by reaction B |

2429.4 J = 16.27 + | heat released by reaction B |
| heat released by reaction B | = 2413.13 J
Number of moles of CHCl2COOH
moles of H3O+ + moles of DCA = CNaOH * VNaOH
2.9*10-4 + moles of DCA = (0.907M)*(0.05L)

= 0.0451
Therefore 4.51*10-2 moles of DCA produces 2429.4 J of heat.
Molar enthalpy of neutralization of CHCl2COOH
2429.4 J * (1/0.0451 mol) = 53866.96 J/mol = 53.87 kJ/mol
Therefore the molar enthalpy of neutralization of dichloroacetic acid is -53.87 kJ/mol.
The H3 for ionization of CHCl2COOH
H3O+(aq) + OH- 2H2O(l) - H1 = 56.12 kJ/mol
CHCl2COOH + OH- + H2O(l) CHCl2COO- + 2H2O(l) - H2 = -53.87 kJ/mol
CHCl2COOH + H2O H3O+ + A- - H3
H3 = H2 H1
= -53.87 kJ/mol (- 56.12 kJ/mol )
= 2.25 kJ/mol
Therefore the molar enthalpy of ionization of DCA is 2.25 kJ/mol.
Go of CHCl2COOH
Go = -RT ln Ka
= - (8.314 * 10-3 ) * (22 + 273 K) * [ln(5.62*10-2)]
= - 7.06 kJ/mol
Therefore the Go is 7.06 kJ/mol.
So of CHCl2COOH
Go = Ho - TSo
7.06 kJ/mol = 2.25 kJ/mol 295 K *So
So = -0.016 kJ/mol K = - 16.31 J/mol K
Therfore the So is -16.31 J/mol K.