Experiment 9

Thermochemistry:
Application of Hesss Law
and the Enthalpy of
Formation of Magnesium Oxide

Purpose:
Using Hesss Law and simple calorimetry, the enthalpy of formation for magnesium oxide
(HfMgO) can be determined to a first approximation.

Background:
An understanding of the heat changes that accompany a chemical reaction is of fundamental
importance in chemistry. Energy changes that occur during ordinary chemical reactions can be
complex. Chemical reactions involve the breaking of chemical bonds in a given set of reactants,
and the formation of other different chemical bonds in a given set of products. A thorough
examination of the many roles that energy changes have in chemical processes can lead to
insights into other chemical phenomena, such as:

Chemical Kinetics - - the physical mechanisms whereby reactants are converted to

products.
Reactions Rates - - the speed of a given process that converts reactants into products.
Chemical Thermodynamics - - the changes in energy that occur during chemical processes
as a function of absolute temperature.
A common measurement used when discussing the relationship between energy and
chemical changes is the enthalpy change for a chemical process, H. The enthalpy change of a
chemical reaction is defined as the amount of heat exchanged by that chemical reaction
conducted at a constant pressure. It is a measure of the difference between the heat contents of
the products and the reactants.
Hrxn = Hfinal - Hinitial = Hproducts - H reactants

A chemical reaction occurs within a focused finite part of the universe, an environment
called a system. Any energy released in the reaction or absorbed in order to initiate the
reaction comes from an external environment called the surroundings. Thus, the reactants and
products constitute the system and everything else, such as the reaction container, room, etc.
make up the surroundings.

The sign of the quantity H indicates the general direction of the energy flow into or out of a
reaction system. If H has a negative sign, heat has been transferred from the system to the
surroundings in an exothermic reaction. If H has a positive sign, heat has been transferred
from the surroundings to the system in an endothermic reaction
Enthalpy, along with internal energy (E) and entropy (S) are referred to as being state
functions. In thermodynamics, a state function, function of state, state quantity, or state
variable is a property of a system that describes quantitatively the equilibrium of the system
irrespective of how the system arrived in that state. Thus, the temperature, pressure, and volume
of a system would also be considered state functions.
Enthalpy is also an extensive property, which means the amount of energy exchanged in
the reaction is a function of the amount of substance being investigated.
Enthalpy is itself a general term for heat transfer. In the context of chemical reactions, it is
common to be able to measure the following types of heat transfer.

Enthalpy of Formation (Hf): The quantity of heat involved when forming 1 mole of a
given substance in its standard state, directly from the elements that comprise the
substance in their standard states (STP).
Enthalpy of Combustion (H): The quantity of heat transferred per mole of a combustible
substance, upon its reaction with excess oxygen, i.e., burning.
Enthalpies of Solution (Hsol), Vaporization (Hvap), Fusion (Hfus), or Sublimation
(Hsub): The quantity of heat involved when a substance changes its physical state
(phase) as it melts, vaporizes, dissolves in water, or changes directly from a solid to a gas.
Enthalpy of Neutralization (Hn): The quantity of heat involved when 1 mole of water is
produced by the reaction of an aqueous acid and an aqueous base, in water.

Enthalpy, Internal Energy, and Heat

Enthalpy is a measure of the total energy of a thermodynamic system; the energy
transferred between the system and its surroundings. It includes the internal energy, E, which
is the energy required to create a system, and the amount of energy required to make room
for it by displacing its environment and establishing its volume and pressure, i.e. the work
(w) involved.

H = E + w = E + PV
The internal energy of a system, E, is precisely defined as the heat at constant pressure
(qp) plus any work (w = PV) done by the system.
E = q p + w = q p + (- PV)

Internal Energy used to expand volume by increasing pressure is lost to the surroundings,
thus the negative sign in the work term.
Thus,

q p = E + PV

and

H = q p

at constant pressure

Hesss Law
This experiment is designed to test and verify Hesss Law; which stated in words says:
The total energy change for any process that consists of a series of
steps is equal to the sum of the enthalpies of the individual steps.
Thus for a given reaction that can be expressed as the sum of four intermediate reactions,
Hesss Law would look something like this:

reaction #1 ----------- > H1

reaction #2 ----------- > H2
reaction #3 ----------- > H3
reaction #4 ----------- > H4
Htot = sum of Hs of individual reactions = H1 + H2 + H3 + H4
Heat of Reaction and Heat of Formation
The total enthalpy change for a reaction involving several steps or multiple reactions
requires the determination of the individual H values. This can be done in two ways:
1) Measuring the heat of reaction using a calorimeter.
2) Tabulating the heat of reaction for a compound formed from its uncombined
elements.

Heat of Reaction (experimental)

In order to measure the heat of reaction of a substance utilizing non-standard amounts of
reagents, it is necessary to determine the actual heat generated in the reaction. The total heat
change (qp) for a reaction carried in a calorimeter at constant pressure is defined as the
product of the mass of material present (m, in grams), the specific heat capacity of that
o
material (Cp, in J/g C), and the change in temperature (t) during the reaction.
q rxn = m Cp T

The heat value, qrxn, is based on the actual amount of material present. The enthalpy
change of the reaction (Hrxn) is based on the amount of heat generated per mole of
substance. Thus, under conditions of constant pressure, as in this experiment:

H rxn =

q rxn
# moles limiting reagent

Example:
How much heat is generated when 0.500 g calcium oxide (CaO) is placed in 50.0
o
mL of water (H2O) in a Styrofoam cup at 23.5 C and the temperature increased to
o
27.0 C?
balanced chemical equation:
CaO(s) + H2O(l) Ca(OH)2 (aq)

mass of calcium = 0.500 g

mass of water is calculated from its volume and density (0.998 g/ml)
mass of water = 50.0 mL * 0.998 g/mL = 49.9 g
mass of the system is the mass of calcium plus the mass of water
mass of system = 0.500 + 49.9 = 50.4 g
o

temperature change (T) = 27.0 C - 23.5 C = 3.5 C

specific heat of water = 1.00 cal/g deg = 4.184 J/g deg
heat of reaction: qrxn =

q rxn = 50.4 g

Cp

4.184 J
3.5 deg = 738 J = 0.738 kJ
g deg

The Heat of Reaction (Hrxn in kJ/mol), is the Heat Evolved adjusted to

reflect the amount of heat that would have been generated by 1 mole of the
reactant.

heat evolved (kJ)

mol wgt calcium oxide (g / mol) = kJ / mol
mass of calcium oxide (g)
0.738 kJ
=
56.08 g / mol = 82.8 kJ / mol
0.5000 g CaO

H rxn =

Since heat was liberated to the surroundings, an exothermic reaction, the products
must contain less energy than the reactants. By convention then, Hrxn must be
written as 82.8 kJ/mol.

Heat of Formation (tabulated)

If one or more of the intermediate reactions involves the formation of a compound from its
uncombined elements, the heat of formation of the compound can be computed from Standard
Heats of formation, symbolized by H that have been derived and tabulated in reference lists
(see the back of your general chemistry text book). Recall that the heat of formation for an
uncombined element is by definition, zero (0).
The standard enthalpy of formation or standard heat of formation of a compound is defined
as the change of enthalpy from the formation of 1 mole of the compound from its constituent
o
elements, with all substances in their standard states at 1 atm (101.3 kPa) and 25 C (298 K).
For example, the heat of reaction to produce calcium oxide from its elements calcium and
oxygen is just the heat of formation of calcium oxide.

1
O 2 (g) CaO(s)
2
= H of (product - CaO) - H of (reactants - Ca + O)

Ca o (s) +
H o rxn

H o rxn = - 635.1kJ / mol - (0 + 0) = - 635.1 kj / mol

The negative sign for the heat of formation value indicates the reaction is exothermic; energy is
released to the surroundings.
The other compound needed in our original reaction is water. Its heat or formation from
hydrogen and oxygen is -285.8 kJ/mol.
Thus, the heat of formation for Ca(OH)2 (aq) can now be computed.
CaO(s) + H2O(l) Ca(OH)2 (aq)

H (kJ/mol
H

-635.1

-285.8

-1002.8

(kJ/mol = (-1002.8) - (635.1 - 285.8) = -81.8 kJ/mol

The difference between the tabulated and experimental heats of reaction is due to experimental
error. A percent error can be calculated.

The Experiment:
The goal of this experiment is to determine the heat of formation of magnesium oxide
(MgO), using calorimetry and Hesss Law. The experimental result will be compared to the
known heat of formation (H ) and the percent error calculated.
The Hesss Law components will consist of three reactions. The first two will involve the
calorimetric determination of the heats of reaction for the reaction between magnesium (Mg)

metal and hydrochloric acid and the reaction between magnesium oxide (MgO) and hydrochloric
acid.
+ 2HCl(aq)

MgCl2 (aq) + H2(g)

Hrxn (A)

(1)

MgO(s) + 2HCl(aq)

MgCl2(aq)

Hrxn (B)

(2)

Mg(s)

+ H2O(l)

The 3rd reaction requires the standard heat of formation, H (kJ/mol) for the formation of
water from hydrogen and oxygen.
H2

+ O2

H)f(H2O)

H2O

(3)

The net reaction for the formation of magnesium oxide (MgO) from magnesium (Mg) and
oxygen (O) is obtained from the summation of reactions 1 ,2, and 3. Before the summation can
be done, the equations must balanced and, if necessary, reversed in order to cancel out all
intermediate components that do not participate in the net equation. The only change in this
regard is to reverse equation 2. As a result of this reversal, the sign of the Hrxn (B) value must
also be reversed.
Mg(s)

+ 2HCl(aq) MgCl2 (aq) +

MgCl2(aq)

+ H2O(l)

MgO(s)

H2

+ O2

+ O2

Mg(s)

Hrxn (A)

(1)

Hrxn (B)

(2)

H2O(l)

(H2O)

(3)

MgO(s)

(MgO)

(4)

H2(g)

+ 2HCl(aq)

The Heat of Reaction for the formation of MgO, H (MgO), from oxygen and magnesium is
computed from the individual heats of reaction from reactions 1, 2, 3.
(H)f (MgO) = H1 + H2 + H3
Note: The reactions of both Mg and MgO with HCl result in the release of hydrogen and
heat; thus, they are exothermic reactions and the Hrxn values are negative. However,
since reaction (2) was reversed, the original Hrxn (2) value must also be reversed,
i.e., it is now positive.
The standard heat of formation for water, H
reference tables. Its value is -285.8 kJ/mol

(H2O)

(3), is obtained from standard

Since H usually does not change significantly with temperature and the data will be
o
o
obtained at close to standard conditions (1atm, 25 C), Hs and H s can be used
interchangeably.

Sample Calculation:
Assume the H(1) and H(2) values from the calorimeter measurements were
-496 kJ/mol and -195 kJ/mol, respectively. Taking into account the reversal of the 2nd reaction,
the overall Hesss Law expression for the Hf of magnesium oxide from its elements would look
like the following:
Hf (MgO) = H1 + (-H2) + H3
Hf (MgO) = -496 kJ/mol +
Hf (MgO) = -586.8 kJ/mol

195 kJ/mol

+ (-285.8 kJ/mol)

(actual value = -601.8 kJ/mol)

Pre-Lab Report & Notebook:

Download from the department data base to your hard drive or flash drive a copy of the
lab report template and the data summary table for the Hesss Law experiment.
http://chem.gmu.edu/templates
Print the summary results tables for the Hesss Law experiment.
Prepare the Pre-lab report according to instructors instructions.

Materials and Equipment:

Materials

Equipment

Styrofoam cups (2), with plastic cover

weighing tray
magnesium metal
magnesium oxide
hydrochloric acid, 1 M

thermometer
metal spatula or glass stirring rod
electronic balance
calculator

Procedure:
1. Obtain 2 Styrofoam cups and plastic cover with hole
2. Form a calorimeter by placing one cup into the other cup
3. Add about 100 mL (precisely measured to nearest 0.1 mL) of 1.00 M HCl to the
calorimeter
Note: Hydrochloric acid is in excess and 100 ml of the acid should be sufficient for all 4
samples (2 samples of magnesium metal and two samples of magnesium oxide).
4. Cover the calorimeter and place a thermometer through the hole in the cover
5. Record and continue to monitor the temperature of the solution
6. Weigh out about 0.2 g of Magnesium (Mg) metal precisely measured to the
nearest 0.001 g

7. Add the metal to the calorimeter all at once and quickly cover the calorimeter
8. Stir the mixture with gentle swirling
9. Monitor the temperature of the solution until a temperature maximum has been reached
10. Record the final temperature
11. Repeat this process for a 2nd weighed sample of Magnesium
12. Weigh out a sample of about 0.5 g of Magnesium Oxide (MgO) precisely measured to the
nearest 0.001 g
13. Add the MgO to the HCl solution
14. Stir the mixture with gentle swirling
15. Monitor the temperature of the solution until a temperature maximum has been reached
16. Record the final temperature
17. Repeat the process for a 2nd sample of MgO
18. Clean out the reaction vessel, flushing the solution down the drain with water

Calculations:
Compute the heat of reaction (qrxn) for each trial.
q rxn = m Cp T

Where: m

= mass of the system (metal + HCl soln)

Cp = Specific Heat of HCL soln (water) = 4.184 J/g-deg

T = Change in temperature
Note: The aqueous hydrochloric acid solution is the absorbing mass in the calorimeter, but
it can be assumed that the specific heat is the same as for water, i.e., both water and
HCl absorb the same amount of heat per gram of their mass for each degree of
temperature change.
Compute the moles of each reactant.
moles =

mass
mol wgt

Verify that the limiting reagent in each reaction is magnesium and magnesium oxide,
respectively.

a. Reaction molar ratio: Mg : HCl = 1:2

b. Actual molar ratio
actual molar ratio =

moles magnesium
moles HCl

c. If the actual molar ratio < reaction molar ratio; then Mg is limiting

Compute the enthalpy of the reaction (Hrxn) for each trial

H rxn =

q rxn
# moles limiting reagent

Compute the average Hrxn for magnesium and magnesium oxide.

Compute the heat of reaction for the formation of MgO, H
H

(MgO),

(MgO),

= sum of Hs of individual reactions = H1 + H2 + H3

H

(MgO)

= H (1) + H(2) + H

(3)

Data Processing:
Use the printed Pre-lab as the laboratory notebook to record the experimental results of
the experiment in the appropriate procedure results block.
Follow the instructions below to populate the spreadsheet file and setup the algorithms for the
Hesss Law computations.
Summarize the measured and computed laboratory results in the printed copy of the
Hesss Law Results Summary Table.
If required by the instructor, transfer the laboratory results to the electronic files and finalize the
laboratory report.

Spreadsheet Processing:
Use a lab computer computers and the web-based data entry form as shown in Figure 9.1
below to enter the Hesss Law laboratory results into an Excel spreadsheet.

Figure 9.1: Input form for entering Hesss Law results into an Excel data base

Class Data Retrieval:

Retrieve class data for Hesss Law experiment from website
http://chem.gmu.edu/results

(select Heat of Formation)

Save the spreadsheet on your hard drive or flash drive with an appropriate file name.
The data will be presented in the RawData sheet in the following columnar setup:

Col
Row

Chemistry 211 Section 205

1
2

Name

m1_Mg initT1_Mg fnlT1_Mg

o
o
g
C
C

V1_Mg
mL

ID

3
4

Col
Row

V2_Mg
mL

m2_Mg
g

initT2_Mg
o
C

fnlT2_Mg
o
C

V1_MgO
mL

m1_MgO
g

initT1_MgO

fnlT1_MgO

V2_MgO
mL

m2_MgO
g

1
2
3
4

Col
Row
1
2

initT2_MgO fnlT2_MgO

3
4

Column Definitions for RawData sheet:

Col A

Student Name

Col B
Col C & G
Col D & H
Col E & I

Student ID
Volume of HCl in reaction A trials 1 & 2
mass of magnesium in reaction A trials 1 & 2
initial temperature in reaction A trials 1 & 2

Col F & J
Col K & O
Col L & P
Col M & Q
Col N & R

final temperature in reaction A trials 1 & 2

Initial volume of HCl in reaction B trials 1 & 2
mass magnesium oxide in reaction B trials 1 & 2
initial temperature in reaction B trials 1 & 2
final temperature in reaction B trials 1 & 2

Create a second Excel sheet and rename it Results Mg.

Col
Row
1

Name

3
4

Schornick, James C.

Col
Row
1
2

Chem 211 Section 205 Hesss Law

dt1
mHClsoln1 molMg1
mHClsoln2
o
g
mol
g
C

molMg2
mol

dt1
o
C

heat1
kJ

heat2
kJ

dH1
kJ/mol

dH2
kJ/mol

dH.rxn.A
kJ/mol

3
4
Column Definitions for ResultsMg sheet:
Col A
Col B & E

Student Name
mass of HCL solution for Magnesium reaction trials 1 & 2

Col C & F
Col D & G
Col H & I
Col J & K
Col L

moles of Mg trials 1 & 2

temperature change (T) in Mg reaction trials 1 &l 2
heat evolved in kJ in Mg reaction trials 1 & 2
enthalpy (H) heat evolved in kJ/mol
Average heat of reaction for Mg reaction (A)

Algorithms to insert into applicable ResultsMgcells:

Select cell A3
Enter: RawData!A3
Select cell B3
Enter: =RawData!C3*1.016
Select cell C3
Enter: =RawData!D3/24.305
Select cell D3
Enter: = RawData!F3-RawData!E3
Select cell E3

Transfers student name from

RawData Sheet
Mass HClst from volume and
density 1 trial
Moles of Mg from Mass
of Mg
& Mol Wgt of Mg 1st trial
temperature change 1st trial

Enter: = RawData!G3*1.016
Select cell F3
Enter: = RawData!H3/24.305
Select cell G3
Enter: = RawData!J3-RawData!I3
Select cell H3
Enter: =(B3+RawData!D3)*4.1814*D3/1000

mass HCl 2nd trial

moles Mg 2nd trial
temperature change 2nd trial
Heat of reaction (qrxn) from Mass
of system (m), specific heat of
HCL(Cp) and change in
Temperature (T)

Select cell I3
Enter: =(E3+RawData!H3)*4.1814*G3/1000 heat 2nd trial
Select cell J3
Enter: =H3/C3
Enthalpy of Reaction (Hrxn), from
heat (qrxn) & # moles
Select cell K3
Enter: =I3/F3
Enthalpy of Reaction trial 2
Select cell L3
Enter: =AVERAGE(J3:K3)
Average Enthalpy of Reaction
Transfer algorithms to all students
Select cells A3:Lx
x = row number of last student
From Editing box under Home on Menu bar select Fill Down
Create a third Excel sheet and rename it ResultsMgO.

Col
Row
1

Chem 211 Sec 205 Hesss Law

dt1
mHClsoln1 molMg1
mHClsoln2
o
g
mol
g
C

Name

F
molMg2
mol

3
4

dt1
o
C

heat1
kJ

heat2
kJ

dH1
kJ/mol

dH2
kJ/mol

dH.rxn.B
kJ/mol

dH.rxn dH.f
kJ/mol kJ/mol

%
Error

Column Definitions for ResultsMgO Sheet:

B&E: mHCLsoln1, mHClsoln2
C&F: molMg1, molMg2
o
o
D&G: dT1 C, dT2 C
H&I:

heat1, heat 2

J&K: dH1, dH2, kJ/mol

L:
dH.rxn.B, kJ/mol
M:
dH.rxn, kJ/mol
N:
O:

dH.f.MgO, kJ/mol
% Error

= mass of HCL solution for MgO reaction

trials 1 & 2
= moles of MgO
= temperature change (T) in MgO reaction
trials 1 & 2
= Heat evolved in kJ in MgO reaction
trials 1 & 2
= Heat evolved in MgO reaction in kJ/mol
= Average heat of reaction for MgO reaction(B)
= Combined Heatrxn of Mg and MgO reactions
(A & B)
= Experimental Heat of formation for MgO
= % Error of the heat of Formation of MgO
compared with the literature value

Algorithms to insert into applicable ResultsMgO cells:

Select cell A3
Enter: =RawData!A3
Select cell B3

(Transfers student name from RawData Sheet

Enter your algorithm to compute the mass of HCl from volume and density for the
1st trial
Select cell C3
Enter your algorithm to compute the moles of MgO for the 1st trial
Select cell D3
Enter your algorithm to compute the temperature change for the 1st trial
Select cell E3
Enter your algorithm to compute the mass of HCL for the 2nd trial
Select cell F3
Enter your algorithm to compute the moles MgO for the
2nd trial
Select cell G3
Enter your algorithm to compute the temperature change for the 2nd trial
Select cell H3
Enter your algorithm to compute the Heat of reaction (qrxn) from Mass
of system (m), specific heat HCL(Cp) and change in Temperature (T) for the 1st
trial
Select cell I3

Enter your algorithm to compute the Heat of reaction (qrxn) from Mass
of system (m), specific heat HCL(Cp) and change in Temperature (T) for 2nd
trial
Select cell J3
Enter your algorithm to compute the Heat evolved in the MgO reaction in
kJ/mol for the 1st trial
Select cell K3
Enter your algorithm to compute the Heat evolved in MgO reaction in
kJ/mol for the 2nd trial
Select cell L3
Enter your algorithm to compute the Average heat of reaction for MgO
for reaction (B)
Select cell M
Enter your algorithm to compute the Combined Heatrxn of Mg and MgO
for reactions A & B
Select cell N
Enter your algorithm to compute the Experimental Heat of formation
for MgO
Select cell O
Enter your algorithm to compugte % Error of the heat of Formation of MgO
compared with the literature value
Transfer algorithms to all students
Select cells A3:Ox

x = row number of last student

From Editing box under Home on the Menu bar select Fill Down

Hesss Law Results Summary Table

Density 1.0 M HCl Soln

g/ml
Mg 1st

J/gdeg

Specific Heat HCl Soln

Mg 2nd

MgO 1st

MgO 2nd

Volume HCl soln

ml

ml

ml

ml

Mass HCl soln

Mass Mg & MgO

Tempinitial

Tempmax

Tempchange (T)

Insert reaction

(2) here

Hrxn (A)

(1)

Insert reaction

(2) here

Hrxn (B)

(2)

Insert reaction

(3) here

Hrxn (H2O) (3)

Insert net reaction (4) here

Hrxn (MgO) (4)

Hesss Law Computation Summary

Show the calculations for the heat evolved (qrxn):
Mg (1)

Insert calculation here

kJ

Mg (2)

Insert calculation here

kJ

MgO (1)

Insert calculation here

kJ

MgO (2)

Insert calculation here

kJ

Show the calculations of Hrxn for Mg and MgO:

Mg (1)

Insert calculation here

kJ/mol

Mg (2)

Insert calculation here

kJ/mol

MgO (1)

Insert calculation here

kJ/mol

MgO (2)

Insert calculation here

kJ/mol

MgO =

kJ/mol

Avg Hrxn

Mg =

kJ/mol

Exp Hf(MgO) = H1(A) + (-H2(B) + (H)3(H2O) =

kJ/mol

Accepted Value Hf(MgO)

kJ/mol

% Error =

Insert calculation here

Insert calculation here