Chapter 6

Thermochemistry
Objectives
-I can define temperature and state the units in which
it is measured.
-I can define heat and state its units.
-I can perform specific-heat calculations.
-I can explain enthalpy change, enthalpy of reaction,
enthalpy of formation, and enthalpy of combustion.
-I can solve problems involving enthalpies of
reaction, enthalpies of formation, and enthalpies of
combustion.
Thermochemistry
Lesson Protocol
Good morning, everyone.
Today, we will do the following:
1. Register for the session, using the Attendance icon 
2.Today, the title of our lesson is “Thermochemistry.”
3. First , we will describe the nature of Energy.
4. Next, we will explain Enthalpy and Calorimeter.
5. Later, we will calculate the enthalpies change using
Hess’s Law and standard enthalpies of formation.
6. Then, each student will interactively answer questions
on  pear deck.
Thermochemistry

The study of energy released or absorbed (heat) during

chemical and physical processes.

We also talk about work (which extends our study into

thermodynamics a bit!)

Examples
• How does burning gasoline “drive” a car?
• How does melting ice cool your drink?
Capacity to do work or transfer energy (heat)

Mechanical Energy: Total PE and KE of system

•Potential energy: energy due to position/forces; stored energy
•Kinetic energy: energy due to motion
•Associated with object “as a whole” (macroscopic)

Example: a ball thrown up in the air

•PE due to position (gravity/height above ground)
•KE due to motion (1/2 m v2)
Total KE and PE of the molecules of an object/system

Potential Energy
•energy stored in chemicals as a result of their composition/bonds

Kinetic Energy
•thermal energy (“heat”)
•related to motion of particles (atoms/molecules)

Example: A mixture of gasoline and oxygen

•PE due to chemical reaction “potential”
•KE due to motion of the molecules
System: The part of the Universe under study

Surroundings: The rest of the universe with which the

system can exchange energy or matter

Open System (e.g. beaker)

• Energy and matter can both flow between system and surroundings

Closed System (e.g. stoppered flask)

• Energy can flow, but no material exchange

Isolated System (e.g. Thermos)

• Neither mass nor energy can be exchanged
Exothermic: process that loses heat (q) to the surroundings
Endothermic: process that absorbs heat (q) from the surroundings

DEMOS: CaO in water/eggs; ammonium nitrate/barium hydroxide

Heat, Work, and Internal Energy
Law of Conservation of Energy
• energy cannot be created or destroyed
• can only be transferred or changed into different forms
Internal Energy (E)
• sum of the kinetic and potential energies of all the “particles” in the system.
• compare the internal vs. mechanical energy of a ball falling through the air.
Heat (q) = thermal energy
• Energy transferred due to a difference in temperature
Work (w) = mechanical energy
• Energy transferred by applying a force through a distance

Temperature vs Heat: What is the difference?

Important Point!

Work can be converted to heat (using the brakes to stop a car)

Heat can be converted to work (an internal combustion engine)

Which seems more efficient / easier to do?

Ethanol Cannon, Rijke Tube, Stirling Engine Demos

Change in internal energy (ΔE) is equal to heat (q) gained
or lost, and work (w) done on or by the system.
• ΔE = q + w
System gains internal energy: ΔE = +
• q = + (heat flows into system from surroundings: Tsys < Tsur)
• w = + (work done on system by surroundings)

System loses internal energy: ΔE = -

• q = - (heat flows out of system to surroundings: Tsys > Tsur)
• w = - (work done by system on surroundings)
• Calculate the delta E for a system undergoing an
exothermic process in which 10 kJ of heat is used and
11000 J of work is done on the system.
• No temperature differences within system
• Temperature of system = Temperature of surroundings
• No more net heat flow
• Example: A cup of hot coffee loses heat to the
surroundings until it reaches room temperature
For chemical reactions, the only work we consider for now is by
a gas expanding against an external (atmospheric) pressure
• w = - PΔV (at constant pressure)
• Derivation
• w = - F x d (work = force times distance)
• F = P x A (force = pressure times area)
• w = - P x A x d = PV

System expands: work is done by system on surroundings

• w = - (system loses energy) e.g. A BALLOON INFLATING
System contracts: work is done by surroundings on system
• w = + (system gains energy) e.g. A GAS BEING COMPRESSED

Units of work/energy
• 1 L.kPa = 1 Joule (J)
• 1 L.atm = 101.3 Joules
How much work (in kJ) is done on a gas that is
compressed from 29.1 L to 11.2 L with a constant
pressure of 1.00 atm?

A sample of an ideal gas at 12.0 atm and 8.00 L is allowed

to expand against a constant external pressure of 2.00 atm.
Calculate the work in kJ done by the gas expansion.
(note: P always refer to the external pressure)
• Find ΔE when a gas absorbs 22 J of heat and has 15 J of work done
on it.

• Find q when 83 J of work are done on a system and its total energy
is increased by 68 J.

• Inside a flexible container, a reaction occurs that releases 3.98 kJ of

heat. It also releases a gas, expanding the container from 1.2 L to
14.8 L against a constant atmospheric pressure of 1.05 atm.
Calculate the internal energy change, in kJ, of the system.
Enthalpy (H) => state property
• Heat measured at constant pressure
• Accounts for PV work
• Depends only on initial and final state of system

ΔH = ΔE + PΔV
• enthalpy change measures heat change at constant pressure
• ΔH = qP
• ΔH = + endothermic process
• ΔH = - exothermic process

ΔE = energy system needs to exist at temperature T

PΔV = work done against the atmosphere to “make
room” for the system
calorie (cal): quantity of heat that raises the
temperature of 1 gram of water by 1oC

Calorie (food calorie) = 1Kcal = 1000cal

SI Unit: Joule (J)

1cal = 4.184J

1 kJ = 1000 J
Heat capacity = amount of heat required to change
an object’s temperature by 1oC

• q = C x ΔΤ
• Q = quantity of heat gained or lost
• C = heat capacity
• ΔT = change in temperature (final T – initial T)

• greater mass = more heat needed (i.e. larger C)

• different substances (composition) have different heat

capacities
Specific Heat Capacity (c): Amount of heat required to raise
temperature of 1 g of substance by 1oC

Molar Heat Capacity (Cn): Amount of heat required to raise

temperature of 1 mole of substance by 1oC

specific heat x molar mass = molar heat

Specific Heat Capacity
q = mcΔT
• q = heat change (J)
• m = mass of substance (g)
• c = specific heat capacity (J/goC)
• ΔT = temperature change (Tf - Ti) (oC)

Molar Heat Capacity

q = nCnΔT
• n = moles of substance (mol)
• Cn = molar heat capacity (J/molK)
What does it mean to have a higher heat capacity? Real world examples?
DEMO: lit match--air balloon vs. water balloon
• Calculate the heat absorbed by 10.5g of water when its
temperature increases from 20.0oC to 80.0oC
Measurement of heat change for chemical and physical
processes.

Calorimeter: device used for measuring heat changes in

chemical and physical processes
A 65.3g piece of metal initially at 100.0oC is dropped into a calorimeter
with 100.0g of water initially at 20.0oC. If the calorimeter water and
metal system come to thermal equilibrium at 24.0oC, what is the
specific heat of the metal?

If 80.00 g of water at 70.00oC is mixed with a 120.0 g of cool water at

20.00oC. What is the final temperature of the mixture. The specific heat
capacity of water is 4.184 J/goC
• Used to measure heat flow in reactions that produce
very high temperatures like combustion
• Calorimeter is calibrated with known reaction
• Find Ccal then use to measure unknown reactions
• qreaction = -qcalorimeter = -Ccal x ΔT

Simulated Experiment
Molar heat of fusion (kJ/mol)
• Heat absorbed in melting one mole of solid at its melting point
• q = nΔHfus

Molar heat of vaporization (kJ/mol)

• Heat absorbed in vaporizing one mole of liquid at its boiling point
• q = nΔHvap

Molar Heat of Solution (kJ/mol)

• Heat change caused by the dissolution of one mole of substance
• q = nΔHsol

Be able to convert each of these to J/g!

Substance MP (K) ΔHfus (KJ/mol) BP (K) ΔHvap (KJ/mol)

Acetone 177.8 5.72 329.4 29.1

Ammonia 195.3 5.65 239.7 23.4
Argon 83.8 1.2 87.3 6.5
Benzene 278.7 9.87 353.3 30.8
Ethanol 158.7 4.60 351.5 43.5
Helium 3.5 0.02 4.22 0.08
Hydrogen 14.0 0.12 20.3 0.90
Methane 90.7 0.94 111.7 8.2
Methanol 175.5 3.16 3372 35.3
Neon 24.5 0.33 27.1 1.76
Nitrogen 63.3 0.72 77.4 5.58
Oxygen 54.8 0.44 90.2 6.82
water 273.2 6.01 373.2 40.7
How many grams of ice at 0oC could be melted by the addition of
2.25kJ of heat?

What amount of heat is released when 145g of steam condenses to

water at 100oC?

*A 50.0g ice cube initially at -10oC is placed in a calorimeter containing

380 g of water at 45oC. cice = 2.2 J/goC
a)Does all of the ice melt?

b)What is the final temperature of the mixture?

ice/water DEMO

Plot of Temperature vs. Time

Shows melting point and boiling point

Temperature remains constant during phase change

Melting point is same as freezing point and boiling point is

same as condensation point
• Change of state depends on direction of heat flow
 vaporization
BP

fusion
MP
 condensation

BP

crystallization

MP
Sketch a labeled heating curve and then calculate the energy required
to convert 150 g of ice at -200C to steam at 130oC given the following :
Substance MP (K) ΔHfus (KJ/mol) BP (K) ΔHvap (KJ/mol)
water 273.2 6.01 373.2 40.7

Substance Specific Heat Capacity

J/goC Cal/goC
Water 4.18 1.00 Superheated steam DEMO
Ice 2.1 0.50
Steam 1.7 0.40
Chemical equation that includes heat (enthalpy) change for reaction as written
• Extensive i.e. more material ⇒ more enthalpy change
• Normal rules of stoichiometry apply to energy as well as mass

Examples:

CaO(s) + H2O(l) => Ca(OH)2(s) ΔH = -65.2KJ

CaO(s) + H2O(l) => Ca(OH)2(s) + 65.2KJ
• How much heat is released by the production of 20.0g Ca(OH)2?

2NaHCO3(s) => Na2CO3(s) + H2O(l) +CO2(g) ΔH = +129KJ

2NaHCO3(s) + 129KJ => Na2CO3(s) + H2O(l) +CO2(g)
• How much heated is used in the decomposition of 0.25 mole of sodium
bicarbonate?
Enthalpy of Combustion
Ethanol (C2H5OH) is a flammable liquid with an enthalpy of combustion of -1368 kJ/mol.

1) Write the balanced thermochemical equation for the combustion of ethanol.

2) Determine what mass of ethanol would be necessary to produce 5,000. kJ by

complete combustion.

3) Determine the mass of oxygen consumed in the reaction.

4) How many kJ would a mixture of 20.0 g of ethanol and 6.0 L of oxygen gas at 25 oC
and 1atm release upon complete combustion?

Whoosh bottle and flaming hands DEMO

Magnitude of ΔH is directly proportional to the amount of
reactant or product

ΔH changes sign when a reaction is reversed

ΔH for a reaction has the same value regardless of the

number of steps i.e. H is a state property
The following reaction is an endothermic process:
• N2 + 2O2 -->2NO2 ΔHo = +68 kJ

If the coefficients are doubled, so is the enthalpy, since

twice as much reactants are being used.
• 2N2 + 4O2 -->4NO2 ΔHo = +136 kJ

If the reaction is reversed, so is the sign of the enthalpy. If the reaction

is endothermic in one direction (takes in energy) it must be exothermic
in the opposite direction (gives off energy)
• 2NO2 --> N2 + 2O2 ΔHo = -68 kJ
If a thermochemical equation can be expressed as the sum
of two or more other equations, the enthalpy of the new
equation is the sum of the enthalpies of the individual
equations.

A + B => C ΔH = 10 kJ
C + B => D + ΔH = 20 kJ
A + 2B => D ΔH = 30kJ
Given:
N2 + O2 --> 2NO ΔHo = 180 kJ
2NO + O2 --> 2NO2 ΔHo = -112 kJ

Find the enthalpy of the following reaction:

2NO2 --> N2 + 2O2 ΔHo = ?
Given the following reactions,
• 2SO2(g) + O2(g) => 2SO3(g) ΔH = -196 kJ
• 2S(s) + 3O2(g) => 2SO3(g) ΔH = -790 kJ

Calculate the heat of reaction for

• S(s) + O2(g) => SO2(g)
Find the ΔH for the reaction below, given the
following reactions and subsequent ΔH values:

2CO2(g)  +  H2O(g)  →  C 2H2(g) +  5/2 O2(g)

C2H2(g) + 2H2(g)  →  C2H6(g)      ΔH  =-94.5 kJ

H2O(g)  →  H2(g) + 1/2 O2 (g)                              ΔH  =71.2 kJ
C2H6(g) +  7/2 O2(g)  →  2CO2(g)  +  3H2O(g)     ΔH  =-283 kJ

answer = 235 kJ
Standard molar enthalpy of formation (ΔHfo)

Enthalpy change when one mole of a compound is formed from its

elements in their standard states.

Standard state: most stable form at 1atm and 25oC

ΔHfo = 0 (by definition) for free elements in their standard state

• O2(g), C(s) (graphite), Fe(s), etc
Ag(s, 25oC) + ½ Cl2(g, 25oC, 1atm) => AgCl (s, 25oC) ΔHo = -127.1 kJ

ΔHfo AgCl(s) = -127.1 kJ/mol

O2(g, 25oC, 1atm) + ½ N2(g, 25oC, 1atm) => NO2(s, 25oC, 1atm) ΔHo = +33.2 kJ

ΔHfo NO2(g) = +33.2 kJ/mol

Enthalpies of Formation: Estimating Enthalpy of Reaction

General Equation
ΔHo = Σ(ΔHof products) - Σ(ΔHof reactants)

(where ΔHof of each substance is multiplied by its coefficient in balanced

equation.)
Ex: Find ΔHo for the reaction 2NO(g) + O2(g) --> 2NO2(g)

Given: ΔHof(NO) = 90.37 kJ/mol ΔHof(NO2) = 33.85

kJ/mol

ΔHo = (33.85 kJ/mol x 2 mol ) – (90.37 kJ/mol x 2 mol + 0)

ΔHo = -113 kJ
More examples
Use the heats of formation data provided to determine the
heat of formation of propane from the following combustion
equation:

C3H8(l) + 5 O2(g) => 3 CO2(g) + 4 H2O(l) ΔHo =-2220kJ

ΔHfo CO2(g) = -394 kJ/mol ΔHfo H2O (l) = -286 kJ/mol

Formation of ions in solution is accompanied by an enthalpy change.

ΔHfo H+(aq) = 0 (defined as a reference point for all other ions to be

measured against.)

When HCl dissolves, HCl(g) => H+ + Cl- ΔHo = -74.9kJ

Use ΔHo = Σ(ΔHof products) - Σ(ΔHof reactants) to find ΔHfo Cl-(aq)

-74.9kJ/mol = {ΔHfo H+(aq) + ΔHfo Cl-(aq)} - ΔHfo HCl(g)

-74.9kJ/mol = 0 + ΔHfo Cl-(aq) + 92.3kJ/mol

ΔHfo Cl-(aq) = -167.2kJ/mol

An engineer is asked to solve the following problem: A water cooling tower contains
2 tons of water (1820 kg) that has frozen solid and is at -30 oC. The ice needs to be
melted and brought to a temperature of 20o by extracting heat from the combustion
reaction between methane and oxygen. If the heat of combustion of methane is -890
KJ/mol, what minimum mass of methane must be burned to accomplish the task?
The relevant constants needed to solve this problem are listed below:

Specific heat capacity of ice 2.10 J/goC

Heat of fusion of water 6.01 KJ/mol
Specific heat capacity of water 4.184 J/goC
State
• A uniquely defined condition of the system
• Specifies composition, temperature, and pressure
State Property
• Depends only on the state of the system
• Path independent (i.e. does not depend on “history” of system)
• A change in a state property depends only on initial and final
conditions, not on how the system reaches those conditions
Example (for discussion)
• Heating 100.0g of liquid water from 30oC to 60oC
State Path
Pressure Work
Volume Heat
Temperature
Density
Enthalpy
Internal Energy
Composition
• Energy change (ΔH) when one mole of bonds is broken
in the gaseous state
• Bond breaking is always endothermic
• H2(g) => 2H(g) ΔH = +436kJ
• Cl2(g) =>2Cl(g) ΔH = +234kJ
• Bond making is always exothermic
• H (g) + Cl(g) => HCl(g) ΔH = -431kJ
• Reaction enthalpies can be estimated with bond energy
changes
A reaction in a rigid container cannot expand significantly,
so no P-V work can be done

From the first law, the total energy change of the system is
the heat flow into or out of the system

wV = 0, qV = ΔE