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General Chemistry II, CHEM-1100

Laboratory Experiment No. 6


Determination of the H of Neutralization
INTRODUCTION
Thermochemistry is the study of the heat evolved or absorbed during a chemical reaction. An
exothermic reaction is said to have a negative H because the reactants lose energy when they form
products. In a constant-pressure or open-cup calorimeter such as the one used in this experiment, the
heat, q, evolved by a chemical reaction is identical to the enthalpy change, H, between the reactants
and products of the reaction. In the specific case of an acid-base neutralization, the enthalpy of
neutralization (Hneutralization) is defined as the heat evolved per one mole of water formed by the
reaction of a mole of acid with a mole of base.
The heat produced or lost by any system during a chemical change can be expressed as
qreaction = - quniverse

(Eq. 1)

where q is expressed in joules. Note that for an exothermic reaction, the heat lost during a chemical
reaction is exactly the same as the heat absorbed by the universe, hence the minus sign in the equation.
For chemical changes that take place inside a calorimeter, the system is considered to be isolated from
the rest of the universe so theoretically, all the energy released by the chemical reaction stays in the
calorimeter. For reactions that take place in solution, the heat of reaction changes the temperature both
of the solution and the calorimeter.
The heat of the reaction is then expressed as
qreaction = - (qproduct solution + qcalorimeter)

(Eq. 2)

The heat absorbed by the reaction solution alone is expressed by


qproduct solution = s m T

(Eq. 3)

where s is the solution specific heat in J/g C, m is the solution mass and T is the temperature
change. Some of the heat given off by the reaction also raises the calorimeter temperature as given by:
qcalorimeter = C T

(Eq. 4)

where C is the calorimeter constant in J/C. The constant C must be determined experimentally for
each individual calorimeter apparatus.
Combining equations (2), (3) and (4) expresses the heat of reaction as:
qreaction = - (s m T + C T)

(Eq. 5)

or in the specific case of this experiment,


qneutralization = - (s m T + C T)

(Eq. 6)

Specific heat and density values for all salt solutions that can be produced in this experiment are listed
in Table 1. Each solution mass will be calculated from the total measured solution volume and the
tabulated solution density. The reaction T is determined from a temperature vs. time graph of the
system where T is measured before and after mixing the reactants. The calorimeter constant in this
experiment is determined from the temperature change that occurs when cold and warm water are
mixed in the calorimeter in the absence of a chemical reaction.
For an acid-base neutralization reaction, the enthalpy of the reaction is called the enthalpy of
neutralization, which is the measured heat of reaction per mole of water formed. This is calculated
using the equation
Hneutralization = qneutralization /mole water formed
(Eq. 7)
The moles of water produced will be calculated from your acid solution volume, its concentration and
the reaction stoichiometry. You will compare your experimental reaction H value with the calculated
reaction H value that you determine from the data in Table 3.
When describing solution concentrations, normality (N, expressed in equivalents per liter) is
sometimes used instead of molarity. This is because some acids such as sulfuric acid donate more than
one mole of protons per mole of acid and some bases such as Ba(OH)2 accept more than one mole of
protons per mole of base. The normality of an acid or base solution is the solution molarity times the
number of protons per mole the acid can donate or the base can react with. A 1.00 M H2SO4 solution is
2.00 N since sulfuric acid is diprotic.
For your experiment you will carry out just one of the reactions listed in Table 1 on the next page.
Your instructor will tell you which one to do. In each case, a 2.00 N acid solution will react
completely with a 2.00 N base solution to give water and the indicated salt. The concentration of each
salt formed will be 1.00 N, not 2.00 N, since the final solution volume is double the initial volume.
Make sure to name your system in your report.
Remember that in each case, moles of water produced equals moles of base used. Also in each case,
0.200 N base equals 0.200 M base. Calculate the moles of base from the molarity of your assigned
base and the volume of base used (always 50.00 mL).

Assigned Reaction Systems: For your experiment, you will be assigned to carry out just one of the
reactions listed in Table 1:
Table 1: Equations for Neutralization Reactions
System No

Neutralization Reaction

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

H3PO4 (aq) + 3 NaOH (aq) Na3PO4 (aq) + 3 H2 O (l)

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

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

HNO3 (aq) + KOH (aq) KNO3 (aq) + H2O (l)

HCl (aq) + KOH (aq) KCl (aq) + H2O (l)

H2SO4 (aq) + 2 KOH (aq) K2SO4 (aq) + 2 H2O (l)

H3PO4 (aq) + 3 KOH (aq) K3PO4 (aq) + 3 H2 O (l)

HNO3 (aq) + NH4OH (aq) NH4NO3 (aq) + H2O (l)

10

HCl (aq) + NH4OH (aq) NH4Cl (aq) + H2O (l)

11

H2SO4(aq) + 2NH4OH(aq) (NH4)2SO4(aq) +2 H2O

12

H3PO4(aq) + 3NH4OH(aq) (NH4)3PO4 (aq) + 3H2 O

Table 2: Specific Heats and Densities of Reaction Product Solutions


System
No

Solution

1
2
3
4
5
6
7
8
9
10
11
12

H2O
Na2SO4
Na3PO4
NaCl
NaNO3
KNO3
KCl
K2SO4
K3PO4
NH4NO3
NH4Cl
(NH4)2SO4
(NH4)3PO4

Salt
Salt
Concentration Concentration
(M)
(N)

0.500
1.00
0.333
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
0.500
1.00
0.333
1.00
1.00
1.00
1.00
1.00
0.500
1.00
0.333
1.00
3

Solution
Specific Heat
(J/g C)
4.184
3.77
3.81
3.89
3.81
3.80
3.87
3.75
3.78
3.86
3.95
3.81
3.86

Solution
Density
(g/mL)
1.00
1.12
1.11
1.04
1.06
1.07
1.05
1.14
1.13
1.04
1.02
1.09
1.08

EXPERIMENTAL
You should not necessarily do the experiments in the order 1, 2, 3. The supply of special thermometers
is limited and there will be a wait for access to the reactant bottles if everyone wants them at the same
time. Its better for half the class to start with Trial 2 which requires acid and base reagents and one
thermometer rather than for everyone to start with Trial 1, which requires two special thermometers
but no reagents.
Trial 1: Calorimeter Constant
Two special 0.01 C thermometers are required for this part, one to monitor the room temperature cup
of water and one for the cup of hot water. Weigh a coffee cup calorimeter (2 nested coffee cups) to
0.001 g. Remove the calorimeter from the balance and pour about 50 mL of room temperature
distilled water from the lab carboy into it. Reweigh the calorimeter containing water to find the mass
of the water. Repeat this process weighing about 50 mL more distilled water into a clean, dry 100 mL
beaker.
Hang a 0.01 C thermometer from a ring stand and clamp with a paper clip so that its bulb is
completely immersed in the calorimeter water without touching the sides or the bottom of the cup.
Heat the water in the beaker on a hotplate with occasional stirring. Measure its temperature with an
ordinary 0.1C thermometer until it reaches about 40C. Place the beaker containing the hot water on
an insulating board or book and suspend a 0.01 C thermometer in it as you did for the calorimeter.
For a 4.5 minute period, use the hanging thermometers to stir and record temperature-time data for the
two containers of water at half minute intervals. Measure both temperatures to 0.01C. At the fiveminute mark, while stirring the water in the calorimeter, rapidly pour the beaker of hot water into the
cold water. Continue to stir occasionally and record temperature-time data for ten more minutes at half
minute intervals.
Trials 2 and 3: Neutralization Reaction
Only one special 0.01 C thermometer is required for this part. Since the acid and base reactant
solutions will have been stored close together for several hours in the same room, you can assume that
the temperature of one is the same as that of the other. You will be assigned one of the chemical
systems listed in Table 1. The acid concentrations are: [HCl] = 2.00M = 2.00N; [HNO3] = 2.00M =
2.00N; [H2SO4] = 1.00M = 2.00N; [H3PO4] = 0.667M = 2.00N. The NaOH, KOH and NH4OH base
concentrations are all 2.00M = 2.00N.
Pipet 50.00 mL of your assigned acid into a clean, dry calorimeter. Pipet 50.00 mL your assigned
0.200 N base solution into a clean, dry 100 mL beaker. Suspend a 0.01 C thermometer from a ring
stand so the thermometer bulb is fully immersed in the acid solution. Since the acid and base solutions
are stored together in the laboratory for several hours before the experiment, you can assume they are
at the same temperature. For a 4.5 minute period, stir occasionally and record temperature-time data
for the acid solution at half-minute intervals.
At the five minute mark, while stirring the acid in the calorimeter, rapidly pour the NaOH solution into
the acid. After the solutions are well mixed, stir occasionally and record temperature-time data for ten
more minutes.
Do a second neutralization reaction, Trial 3 with the same acid-base pair you used in Trial 2.

DIRECTIONS FOR REPORT AND CALCULATIONS


Plot a Temperature vs. Time graph for each of the three trials. Your plots for mixing warm water and
cool water will look like the graph of temperature vs. time shown below. There will be three lines with
a large separation between the plots for hot and cold water. On the other hand, the acid-base
neutralization plots will have one line at room temperature and one line at elevated temperature after
the solutions mix. For each trial, plot the temperature-time data as separate data sets using Excel or
Graphical Analysis and generate separate straight lines with their respective line equations. There will
be three straight lines for Trial 1, and two straight lines each for Trials 2 and 3.
Cooling Curve for Water

Time of mixing

38

Temperature (C)

36
34
32

Tinitial for the warm water

y = mwarmx + bwarm

30

Tfinal for the mixture

28

y = mmixx + bmix

26
24
22

Tinitial for the cool water

y = mcoolx + bcool

20
0

10

11

12

13

14

15

Time (min)

To find the initial temperature for each trial, extrapolate the straight line temperature vs. time plot
before mixing the solutions to the vertical line representing the five minute mixing moment. To find
the final temperature after mixing, extrapolate the straight line plot after mixing back to the five
minute mixing line.
Trial 1: Calorimeter Constant
For Trial 1, use Equation 3 twice, once to calculate heat lost by the warm water and once to calculate
heat gained by the cool water. Heat gained by the cold water equals the original mass of cold water
times the specific heat of water times its temperature change. Heat lost by the hot water equals the
original mass of hot water times the specific heat of water times its temperature change. The two heat
quantities will have opposite signs. You might expect them to have the same magnitude but they will
not. Some heat will be lost to the plastic cup calorimeter. This difference in heat, not temperature,
between the two qsolution quantities is the heat absorbed by the calorimeter. To find the calorimeter
constant in J/C, divide the heat absorbed by the calorimeter by the temperature change (T) of the
cool water.

Trials 2 and 3: H Determination


Using your measured T values and the solution specific heats and densities in Table 2, calculate the
heat gained by the product mixture (qproduct mixture). The heat absorbed by the calorimeter (qcalorimeter)
must be added to the heat gained by the product mixture to find qneutralization. The qcalorimeter value is
obtained by multiplying the calorimeter constant by the temperature change during the neutralization
reaction. From qneutralization, calculate Hneutralization which is the heat of neutralization per mole of water
formed in the reaction.
Using the standard thermodynamic data in Table 3, calculate the theoretical value of Hneutralization for
the system assigned to you. That is, from the sum of the Hf of water and the Hf of salt formed,
subtract the Hf values of the two reactants in your system present at 1.00 N concentration. Compare
this theoretical Hneutralization value with your measured Hneutralization value.
Table 3: Heats of Formation of 1.00 N Solutions of Selected Substances at 25 C
Substance in 1.00 N Solution

Hf (kJ/mol)

H2O
HCl
HClO4
HNO3
H2SO4
H3PO4
NaOH
KOH
NH4OH (or NH3)
NaCl
KCl
NH4Cl
NaClO4
NaNO3
KNO3
NH4NO3
Na2SO4
K2SO4
(NH4)2SO4
Na3PO4
K3PO4
(NH4)3PO4

-285.8
-167.4
-129.3
-207.5
-909.2
-1277.4
-469.4
-479.9
-362.3
-407.1
-418.8
-299.6
-369.4
-446.4
-459.8
-339.7
-1387.0
-1408.8
-1174.4
-1987.4
-2032.9
-1674.9

Reagent Disposal:
Since they contain no heavy metals and are essentially pH neutral, all the salt solutions produced in
this experiment may be poured directly down sink drains without harming the environment. Unused
acid and base solutions, however, violate the pH limits of must municipal sewage systems and must be
disposed of as hazardous waste, preferably by pouring them into the heavy metal waste container
provided in the laboratory hood.
6

Data Table for Calorimeter Constant Evaluation (Trial 1)


Name of Acid-Base System:_____________________________

Time (min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0

Measured Temperature Values


Hot Water
Cold water
Mixture

Mix Solutions

Instructors Initials______________

Data Tables for Reaction H Measurements


Trial 2
Time (min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0 (Mix)
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0

Trial 3

Solution
Temperatures
Acid Solution

Time (min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0 (Mix)
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0

Salt Solution

Solution
Temperatures
Acid Solution

Salt Solution

Instructors Initials_____________

General Chemistry II, CHEM-1100


Report for Laboratory Experiment No. 6
Determination of the H of Neutralization
For full credit, show setups in the space provided. Answers must have the correct units, the correct
number of significant figures and when appropriate, be in proper scientific notation.
1.

Plot temperature vs. time for your three trials and attach the graphs to this report.

2.

Use the information provided on p. 5 to calculate the calorimeter constant of your apparatus.
Show your setup here.
(2 points)

2.

Use Equation 6 to calculate the heat of reaction from your Trial 2.

(6 points)

(3 points)

3.

Use Equation 6 to calculate the heat of reaction from your Trial 3.

(3 points)

4.

Calculate Hneutralization for Trials 2 and 3 and your average Hneutralization.

(3 points)

5.

What is your acid-base system? __________________What is the calculated theoretical


(2 points)
Hneutralization value for your system using data from Table 3?

6.

Calculate the per cent error of your experimental Hneutralization value.


10

(1 points)

General Chemistry II, CHEM-1100


Prestudy for Laboratory Experiment No. 6
Determination of the H of Neutralization
Name_______________________________
A student mixed 100.0 mL of 0.8800 M HCl with 100.0 mL of 0.8800 M NaOH and obtained the
following temperature-time data. Both reactant solutions were the same temperature prior to mixing.
Time (min)
0.0
0.5
1.0
1.5
2.0
3.0
4.0
4.5
MIX
5.5

Time (min)
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0

Temperature (C)
23.25
23.27
23.28
23.30
23.30
23.35
23.44
23.47
28.35

Temperature (C)
28.50
28.55
28.48
28.32
28.25
28.20
28.05
27.96
27.80
27.75

The density of the product mixture was 1.02 g/mL and its heat capacity was 4.02 J/gC. The
calorimeter constant was 52.8 J/C.
1.

Write the balanced equation for the reaction between aqueous HCl and NaOH.

(1 point)

2.
Using Excel or Graphical Analysis, plot Temperature vs. Time. There will be two straight
lines, one before mixing and one after. The former line will allow you to find the initial temperature
and the latter line will give the final temperature.) Find the initial temperature of the acid and base
solutions and the final temperature of the mixture. Determine T for the reaction.
(4 points)

(Prestudy continued on next page)


11

3.

Calculate the heat of neutralization for the experiment.

4.

Calculate the enthalpy of neutralization per mole of water produced in the experiment.
(2 points)

12

(3 points)