Title

Heats of Reactions – Hess’s Law

Objective
To measure experimentally the amount of heats absorbed or released when; solid NaOH is
dissolved in water, solid NaOH is dissolved in a HCl solution and the reaction of NaOH solution
with HCl solution.

Introduction
Thermochemistry is the study of heat change in chemical reactions. A reaction may
absorb or release energy which is measured as enthalpy. However, the absolute value of the
enthalpy of a reaction cannot be measured. This is due to the fact that enthalpy is a state function
and it does not depend on the pathway taken to convert reactants into products. Thus, the
enthalpy change, ΔH of a reaction can be determined. The first law of thermodynamics states
that during a chemical reaction energy is conserved. This application is directly related to Hess’s
Law. Hess’s Law states that when reactants are converted to products, the change in enthalpy is
the same whether the rection takes place in one step or in a series of steps (Chang, 2008). To put
it simple, mathematicians add two or more linear mathematical equations to form a net
equation. This concept can also be applied to the heat of reactions where one or more heat of
reactions can be summed to form a final net heat of reaction.

ΔH1
A C

ΔH2 ΔH3
B

From Hess’s Law: ΔH3 = ΔH2 + ΔH1

As we know, the heat change of a chemical reaction cannot be measured just as it is.
However, the heat released or absorbed during chemical reactions can be indirectly measured
by using a calorimeter by calculating the mass of solution, change in temperature and specific
heat capacity of the solution as follows:

Q = mcΔT
where
q = heat lost or gained
m = mass of solution
c = specific heat capacity of solution (4.18 Jg-1 °C-1)
ΔT = change in temperature (T2 – T1)
 In this experiment, a simple styrofoam calorimeter is used to measure the heat released by
three reactions. According to Hess’s law, when two or more thermochemical equations are
added, the enthalpy change of the resulting equation is the sum of the added equations. The
equations used in this experiment are:
(1) Solid sodium hydroxide dissolves in water to form an aqueous solution of ions:
NaOH(s) → Na+ (aq) + OH- (aq) ΔH1
(2) Solution of aqueous sodium hydroxide and hydrochloric acid reacts to form water and
aqueous sodium chloride:

Na+ (aq) + OH- (aq) + H+ (aq) + Cl- (aq) → Na+ (aq) + Cl- (aq) + H2O(l) ΔH2

(3) Solid sodium hydroxide reacts with hydrochloric acid to form water and aqueous sodium
chloride:

NaOH (s) + H+ (aq) Cl- (aq) → Na+ (aq) + Cl-(aq) + H2O (l) ΔH3

The purpose of this experiment is to measure experimentally the amount of heats absorbed
or released when; solid NaOH is dissolved in water, solid NaOH is dissolved in a HCl solution and
the reaction of NaOH solution with HCl solution.

Apparatus
1. Measuring cylinder [50 mL and 100mL]
2. Beaker
3. Thermometer
4. Glass rod
5. Analytical balance
6. Calorimeter or styrofoam cup

Chemicals
1. Solid sodium hydroxide, NaOH Figure 1
2. 1.0 M sodium hydroxide, NaOH
3. Hydrochloric acid, HCl [1.0 M and 5.0 M]
Procedure
Results
Reaction 1 Reaction 3
NaOH(s) → Na+ (aq) + OH- (aq) NaOH (s) + H+ (aq) Cl- (aq) → H2O (l) + Na+ (aq) + Cl-(aq)

Volume H2O or HCl

100.0 200.0
used (mL)

Mass of solid +
2.13 2.11
container (g)

Mass of empty
0.02 0.02
container (g)

Mass of solid used (g) 2.11 2.09

Final temperature, t2
(°C) 31.0 32.5

Initial temperature, t1
(°C) 26.5 26.0

Change in
temperature, ΔT (°C) 4.5 6.5

Table 1.1: Data recording for Reactions 1 and 3

Reaction 2

Na+ (aq) + OH- (aq) + H+ (aq) + Cl- (aq) → Na+ (aq) + Cl- (aq) + H2O(l)

Volume of NaOH solution

used (mL) 50.0

Volume of HCl solution used

(mL) 50.0

Total volume of solution used

(mL) 100.0

Initial temperature of HCl (°C) 25.4

Initial temperature of NaOH
(°C) 25.6
 Average temperature (°C) 25.5

Final temperature of mixture

32.0
(°C)

Change in temperature, ΔT
6.5
(°C)

Table 1.2: Data recording of Reaction 2

Step Reaction 1 Reaction 2 Reaction 3

NaOH(s) → Na+ (aq) + OH- Na+ (aq) + OH- (aq) + H+ (aq) NaOH(s) + H+ (aq) + Cl- (aq)
- + -
(aq) + Cl (aq) → Na (aq) + Cl (aq) → Na+ (aq) + Cl- (aq) + H2O(l)
+ H2O(l)
Total mass of solid, water or
solution used, m (g) 102.11 100.00 202.09

Change in temperature, ΔT(°C)

4.5 6.5 6.5

Specific heat of water, c

4.18 Jg-1 °C-1 4.18 Jg-1 °C-1 4.18 Jg-1 °C-1

Energy absorbed/lost by the

water (J) 1920.689 2717.00 5490.785

Energy absorbed/lost by the

reaction (J) -1920.689 -2717.00 -5490.785

Energy absorbed/lost (kJ)

-1.921 -2.717 -5.491

Rxn 1: Mass of NaOH used (g)

Rxn 2: Volume of NaOH used (L) 2.11 g 0.05 L 2.09 g
Rxn 3: Mass of NaOH used (g)

Rxn 1: Molar mass of NaOH

(g/mol)
Rxn 2: Concentration of NaOH 40 g mol-1 1.0 mol L-1 40 g mol-1
(mol/L)
Rxn 3: Molar mass of NaOH
(g/mol)
 Moles of NaOH actually used
(mol) 0.0528 0.0500 0.0523

Heat of Reaction H (kJ/mol)

-36.38 -54.34 -104.99

Table 2: Calculation of heats of reaction

Calculation
Reaction 1
Total mass of solution = mass of solid NaOH + mass of water
= 2.11 g + 100.0 g
= 102.11 g

Q water = m c ΔT

= (102.11 g)  (4.18 Jg-1 °C-1)  (4.5 °C)

= 1920.689 J
Qrxn = -1920.689 J
= - 1.921 kJ
Num of moles of NaOH used = mass (g) _
-1
molar mass (gmol )

= 2.11 g _
40 gmol-1
= 0.0528 mol

ΔH = Q rxn (kJ) _
moles of NaOH (mol)
= - 1.921 kJ _
0.0528 mol
= -36.38 kJ mol-1
Reaction 2
Total mass of solution = mass of NaOH + mass of HCl
= 50.0 g + 50.0 g
= 100.0 g

Qwater = m c ΔT

= (100g)  ( 4.18 Jg-1 °C-1)  (6.5°C)

= 2717 J

Qrxn = -2717 J

= -2.717 kJ

Num of moles of NaOH used = volume (L)  molarity (mol/L)

= (0.05 L)  (1.0 mol/L)
= 0.05 mol

ΔH = Q rxn (kJ) _

moles of NaOH (mol)

= -2.717 kJ
0.05 mol
= -54.34 kJ mol-1

Reaction 3
Total mass of solution = mass of solid NaOH + mass of HCl
= 2.09 g + 200.00 g
= 202.09 g

Q water = m c ΔT

= (202.09 g)  (4.18 Jg-1 °C-1)  (6.5 °C)

= 5490.785 J

Qrxn = -5490.785 J

= - 5.491 kJ
 Num of moles of NaOH used = mass (g) _
molar mass (gmol-1)
= 2.09 g _
40 gmol-1
= 0.0523 mol

ΔH = Q rxn (kJ) _

moles of NaOH (mol)

= - 5.491 kJ _
0.0523 mol

= -104.99 kJ mol-1

Discussion
According to Hess’s Law, by adding equations of reaction 1 and 2, we will obtain equation
for reaction 3.

Reaction 1: NaOH(s) → Na+ (aq) + OH- (aq)

Reaction 2: Na+ (aq) + OH- (aq) + H+ (aq) + Cl-(aq) → Na+ (aq) + Cl- (aq) + H2O(l)

Reaction 3: NaOH (s) + H+ (aq) Cl- (aq) → Na+ (aq) + Cl-(aq) + H2O (l)

However, when we mathematically add up enthalpy of reaction 1 and 2,

(ΔH1 + ΔH2) = -90.72 kJ mol-1, ΔH3 = -104.99 kJ mol-1

by comparison, the experimental value of ΔH3 calculated differed from experimental value of (Δ
H1 + ΔH2). This may be due to certain errors done during the experiment such as solid NaOH was
not dissolved properly. If this happened, ΔH would be smaller or less than it should have been
thus causing inaccurate calculation. The percentage difference between ΔH3 and (ΔH1 + ΔH2) can
be calculated as follows:
 Percent Difference = ΔH3 – (ΔH1 + ΔH2)
 100
ΔH3

= -104.99 kJ mol-1 – (-90.72 kJ mol-1)

 100
-104.99 kJ mol-1

= 13.59 %

The percentage difference between ΔH3 and (ΔH1 + ΔH2) holds a 13.59% error compared to the
theoretical value. This may be due to certain errors or improper method done during the
experiment which may include:
i. Uncertainties when taking measurements resulting in random error. This may be due to
the experiment was conducted only once, therefore affecting the accuracy of the result
obtained. This error can be minimized by conducting the experiment several times to
calculate several heats of neutralization of sodium hydroxide with hydrochloric to obtain
the average value.

ii. Heat lost to the surrounding resulting in systemic error. The heat from the Styrofoam cup
calorimeter escaped and exchanged to the surrounding. Thus, to maximize the efficiency
of the calorimeter within the lab, one could include an insulator such as wrapping the
Styrofoam cup with cotton or placing the Styrofoam cup in a beaker wrapped with paper
may reduce the heat lost to the surrounding. Or else, a double Styrofoam cup also
provides good thermal insulation for the system.

iii. Undissolved solid NaOH. During the experiment, there may have been times when the
NaOH did not fully mix, which meant that the reaction did not reach its full potential.
Hence, the wrong temperature could have been recorded during the different time
intervals. To ensure that that the solution fully reacted, the experiment could be recorded
over a longer and consistent time interval. Another way of ensuring that the reaction has
reached its full potential is by mixing the solution with a stirring rod and not the
thermometer. This way we can avoid taking the wrong temperature of the solution.

iv. Inaccurate mass of NaOH. This error may be because NaOH absorbs the water vapour in
the air causing an increase in the mass of NaOH and thus affecting the calculations as well
as the result. This error can be minimized by covering the solid NaOH with a cover to
minimize contact with air while preparing HCl solution. Other than that, the mass of NaOH
 can be measured in an enclosed analytical balance with a glass windshield. This is done
so that contaminates or air do not affect the sample as it is being measured.
An enthalpy diagram can be drawn to illustrate Hess’s Law for neutralization reaction of one mol
of solid sodium hydroxide with hydrochloric acid.

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

ΔH1 = -36.38 kJ mol-1

Enthalpy, H (kJ mol-1)

ΔH3 = -104.99 kJ mol-1 NaOH (s) + HCl (aq)

ΔH2 = -54.34 kJ mol-1

NaCl (aq) + H2O (l)

Reaction progress

Figure 2: Enthalpy diagram of neutralization reaction of NaOH and HCl

Based on the enthalpy diagram, the enthalpy change for NaOH and HCl was in fact negative as it
was observed that the final temperature was greater than the initial temperature. Thus, resulting
in an overall exothermic reaction.

Conclusion
In conclusion, Hess's law can be used to determine the overall energy required for a
chemical reaction. In this experiment, the enthalpy of neutralization of sodium hydroxide with
hydrochloric acid was calculated to be -104.99 kJ/mol-1 whereas the enthalpy of reaction 1 which
is dissolution of NaOH in water was calculated to be -36.38 kJ mol-1 while the enthalpy of reaction
2, solid NaOH dissolved in HCl was calculated to be -54.34 kJ mol-1. The sum of enthalpy of
reaction 1 and 2 is -90.72 kJ mol-1. Thus, the hypothesis of this experiment can be accepted as
the value of (ΔH1 + ΔH2) is somewhat close to the enthalpy value of reaction 3, ΔH3. If the error
in this experiment can be further minimized, thus the value of enthalpy will become more
accurate to one another.
Reference

Material type In-text citation Bibliography

An article (Denton, 2011) Denton, L. (2011, October 6). Top 10 Management Skills You
Need. Lab Product. Vol 6, Issue 8.

An article in an electronic (Nilsson & Niedderer, 2014) Nilsson, T., & Niedderer, H. (2014). Undergraduate students'
journal conceptions of enthalpy, enthalpy change and related
concepts. Chemistry Education Research and Practice, 15(3),
336-353.

An article in an electronic (Sutcliffe, 1983) Sutcliffe, R. (1983). Another method for solving problems
journal based on Hess's law. Journal of Chemical Education, 60(4), 362.

A website (Lufaso) Michael Lufaso. (n.d.). Thermochemistry. Retrieved from,

https://www.unf.edu/~michael.lufaso/chem2045/Chapter5.pdf

A book (Chang, 2008) Chang, R. (2008). General chemistry: the essential concepts.
Boston: McGraw-Hill.

A book (Paul Flowers, 2015) Paul Flowers, W. R. (2015). Thermochemistry. In Chemistry (pp.
231-280). Houston, Texas: OpenStax.