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You are on page 1of 81

and Bruce E. Bursten

Thermochemistry

Thermochemistry

Energy

Work: Energy used to cause an object that

has mass to move.

Heat: Energy used to cause the

temperature of an object to rise.

Thermochemistry

Potential Energy

position or chemical composition.

Thermochemistry

Electrostatic PE

Arises from the interaction between charged

particles.

Eel = k Q1 Q2 k = 8.99x109 Jm/C2

d Q charge of particles

d distance

If charges are same sign they repel and Eel is

positive. If they have opposite sign they

attract and Eel is negative.

The lower the energy of system the more stable

it is. Thus the more strongly opposite charged

Thermochemistry

particles attract each other.

Kinetic Energy

motion.

1

KE = mv2

2

Thermochemistry

Units of Energy

kg m2

1 J = 1

s2

• An older, non-SI unit is still in

widespread use: The calorie (cal).

1 cal = 4.184 J

Thermochemistry

Joule

m/s possesses a kinetic energy of 1 J.

increase the temperature of 1 g of water

from 14.5 0C to 15.5 0C.

• 1 Cal = 1000 cal = 1 kcal

Thermochemistry

System and Surroundings

• Consider the reaction inside

the piston

• 2H2(g) +O2->2H2O(g)+heat

• The system includes the

molecules we want to study

(here, the hydrogen and

oxygen molecules).

Reactants an products.

• The surroundings are

everything else (here, the

cylinder and piston). Thermochemistry

Work

• Energy is used to

move an object over

some distance.

• w = F d,

where w is work, F

is the force, and d is

the distance over

which the force is

exerted.

Thermochemistry

Heat

• Energy can also be

transferred as heat.

• Heat flows from warmer

objects to cooler objects.

• HEAT THE ENERGY

TRANSFERRED

BETWEEN A SYSTEM

AND ITS

SURROUNDINGS AS A

RESULT OF THEIR

DIFFERENCE IN

TEMPERATURE

Thermochemistry

Transferal of Energy

clay is increased when it is moved

from the ground to the top of the wall.

Thermochemistry

Transferal of Energy

clay is increased when it is moved

from the ground to the top of the wall.

b) As the ball falls, its potential energy is

converted to kinetic energy.

Thermochemistry

Transferal of Energy

clay is increased when it is moved

from the ground to the top of the wall.

b) As the ball falls, its potential energy is

converted to kinetic energy.

c) When it hits the ground, its kinetic

energy falls to zero (since it is no

longer moving); some of the energy

does work on the ball, the rest is

dissipated as heat. Thermochemistry

First Law of Thermodynamics

• Energy is neither created nor destroyed.

• In other words, the total energy of the universe is

a constant; if the system loses energy, it must be

gained by the surroundings, and vice versa.

Thermochemistry

Internal Energy

The internal energy of a system is the sum of all

kinetic and potential energies of all components

of the system; we call it E.

Thermochemistry

Internal Energy

By definition, the change in internal energy, E,

is the final energy of the system minus the initial

energy of the system:

E = Efinal − Einitial

Thermochemistry

Changes in Internal Energy

Therefore, the system

absorbed energy from

the surroundings.

Thermochemistry

Changes in Internal Energy

Therefore, the system

released energy to the

surroundings.

Thermochemistry

Changes in Internal Energy

• When energy is

exchanged between

the system and the

surroundings, it is

exchanged as either

heat (q) or work (w).

• That is, E = q + w.

Thermochemistry

E, q, w, and Their Signs

Thermochemistry

Exchange of Heat between

System and Surroundings

• When heat is absorbed by the system from

the surroundings, the process is endothermic.

Thermochemistry

Exchange of Heat between

System and Surroundings

• When heat is absorbed by the system from

the surroundings, the process is endothermic.

• When heat is released by the system to the

surroundings, the process is exothermic.

Thermochemistry

State Functions

Usually we have no way of knowing the

internal energy of a system; finding that value

is simply too complex a problem.

Thermochemistry

State Functions

• However, we do know that the internal energy

of a system is independent of the path by

which the system achieved that state.

In the system below, the water could have reached

room temperature from either direction.

Thermochemistry

State Functions

• Therefore, internal energy is a state function.

• It depends only on the present state of the

system, not on the path by which the

system arrived at that state.

• And so, E depends only on Einitial and Efinal.

Thermochemistry

Work

associated with a

change of

volume ( V) that

occurs against a

resisting pressure.

Thermochemistry

Work

We can measure the work done by the gas if

the reaction is done in a vessel that has been

fitted with a piston.

w = −PV

Thermochemistry

Enthalpy

• If a process takes place at constant

pressure (as the majority of processes we

study do) and the only work done is this

pressure-volume work, we can account for

heat flow during the process by measuring

the enthalpy of the system.

• Enthalpy is the internal energy plus the

product of pressure and volume:

H = E + PV Thermochemistry

Enthalpy

pressure, the change in enthalpy, H, is

H = (E + PV)

• This can be written

H = E + PV

Thermochemistry

Enthalpy

• Since E = q + w and w = −PV, we

can substitute these into the enthalpy

expression:

H = E + PV

H = (q+w) − w

H = q

• So, at constant pressure the change in

enthalpy is the heat gained or lost.

Thermochemistry

Endothermicity and

Exothermicity

• A process is

endothermic, then,

when H is

positive.

Thermochemistry

Endothermicity and

Exothermicity

• A process is

endothermic when

H is positive.

• A process is

exothermic when

H is negative.

Thermochemistry

Enthalpies of Reaction

The change in

enthalpy, H, is the

enthalpy of the

products minus the

enthalpy of the

reactants:

H = Hproducts − Hreactants

Thermochemistry

Enthalpies of Reaction

reaction, or the heat of reaction.

Thermochemistry

The Truth about Enthalpy

2. H for a reaction in the forward

direction is equal in size, but opposite

in sign, to H for the reverse reaction.

3. H for a reaction depends on the state

of the products and the state of the

reactants.

Thermochemistry

Practice problem– Change in enthalpy – Heat of reaction

3CuCl2 + 2Al 3Cu + 2AlCl3 ΔH = -793.5 kJ

6CuCl2 + 4Al 6Cu + 4AlCl3

9 Cu + 6 AlCl3 9 CuCl2 + 6 Al

3. Given the equation at the top of the page, how much energy

will be given off by the reaction of 2.07 g of Al with excess

CuCl2? Thermochemistry

Constant Pressure Calorimetry

By carrying out a

reaction in aqueous

solution in a simple

calorimeter such as this

one, one can indirectly

measure the heat

change for the system

by measuring the heat

change for the water in

the calorimeter.

Thermochemistry

Heat Capacity and Specific Heat

• Calorimeter = apparatus that measures heat flow.

• Heat capacity = the amount of energy required to raise

the temperature of an object (by one degree). (J °C-1)

• Molar heat capacity = heat capacity of 1 mol of a

substance. (J mol-1 °C-1)

• Specific heat = specific heat capacity = heat capacity of 1

g of a substance. (J g-1 °C-1)

Thermochemistry

• Remember a change in T in K and in 0C

are equal in magnitude

• T in K = T in 0C

Thermochemistry

Molar heat capacity

substance. The amount of heat required

to increase the temperature of 1 mole of

substance 1 K.

Thermochemistry

Constant Pressure Calorimetry

• Atmospheric pressure is constant!

mCT mCT

Object 1 Object 2

H qP

qrxn qsoln specific heat of solution

grams of solution T

• HEAT LOST = HEAT GAINED

Thermochemistry

Constant Pressure Calorimetry

heat for water is well

known (4.184 J/mol-K),

we can measure H for

the reaction with this

equation:

q = m s T

Thermochemistry

Heat Capacity and Specific Heat

heat transferred

Specific heat =

mass temperature change

q

s=

m T

Thermochemistry

Sample problem 1

209 J is required to increased the

temperature of 50.0 g of water by

1.00K

s=q / m T

Thermochemistry

Sample Problem 2

250g of water from 25 0C to 75 0C.

• Specific heat of water 4.18 J/gK

• Find the molar heat capacity of water.

Thermochemistry

Sample problem 3

0.100 M HNO3, and the temperature of the mixture

increases from 23.1°C to 49.8°C. Calculate ΔH for

this reaction in kJ mol-1. Assume that the specific heat

of each solution is equal to the specific heat of water,

4.184 J g-1 °C-1.

Thermochemistry

Sample problem 4

An unknown metal is to be analyzed for specific heat.

A 12.84-g piece of the metal is placed in boiling

water at 101.5°C until it attained that temperature.

The metal is then removed from the boiling water

and placed into a styrofoam cup containing 54.92 g

of water at 23.2°C. The final temperature of the

water was 26.1°C. What is the specific heat of the

metal sample, in J g-1 °C-1?

Thermochemistry

Bomb Calorimetry

A more

sophisticated model

is the bomb

calorimeter, it has a

chamber where a

chemical reaction

takes place and a

device to start the

reaction.

Thermochemistry

HEAT CAPACITY OF THE

CALORIMETER

The heat is absorbed by the calorimeter and

the T of the water rises.

• THE HEAT CAPACITY OF THE

CALORIMETER HAS TO BE CALCULATED.

It is done by measuring T in a reaction that

releases a known amount of heat. The heat

capacity of the calorimeter Ccal= amount of heat

absorbed / T

Thermochemistry

Bomb Calorimetry (Constant Volume Calorimetry)

constant volume.

• Use a bomb calorimeter.

• Usually study combustion.

qrxn Ccal T

Thermochemistry

Bomb Calorimetry

is constant, what is measured is really the

change in internal energy, E, not H.

• For most reactions, the difference is very

small.

Thermochemistry

Sample problem 5

A 0.5269 g sample of octane is placed in a bomb

calorimeter with a heat capacity of 11.3 kJ °C-1.

The original temperature of the water in the

calorimeter is 21.93°C. After combustion, the

temperature increases to 24.21°C. Determine the

enthalpy of combustion per mole and per gram of

octane.

Thermochemistry

Sample problem 6

• After 50 mL of 1.0 M HCl and 50mL of 1.0M

NaOH are mixed in a coffe cup calorimeter, the

temperature of the solution increases form 21.0

0C to 27.5 0C. Calculate the enthalpy change for

calorimeter loses only a negligible quantity of

heat, total volume of solution is 100mL, that its

density is 1.0 g/mL and the specific heat is

4.18J/gk

Thermochemistry

Hess’s Law

and it is inconvenient to measure H

for every reaction in which we are

interested.

• However, we can estimate H using

H values that are published and the

properties of enthalpy.

Thermochemistry

Hess’s Law

“If a reaction is carried

out in a series of

steps, H for the

overall reaction will be

equal to the sum of

the enthalpy changes

for the individual

steps.”

Thermochemistry

Hess’s Law

Because H is a state

function, the total

enthalpy change

depends only on the

initial state of the

reactants and the final

state of the products.

Thermochemistry

Example

The bombardier beetle uses an explosive discharge as

a defensive measure. The chemical reaction

involved is the oxidation of hydroquinone by

hydrogen peroxide to produce quinone and water:

C6H4(OH)2 (aq) + H2O2 (aq) C6H4O2 (aq) + 2 H2O (l)

Thermochemistry

C6H4(OH)2 (aq) C6H4O2 (aq) + H2 (g) ΔH = +177.4 kJ

H2 (g) + O2 (g) H2O2 (aq) ΔH = -191.2 kJ

H2 (g) + ½ O2 (g) H2O (g) ΔH = -241.8 kJ

H2O (g) H2O (l) ΔH = -43.8 kJ

ΔH = ???

Thermochemistry

Enthalpies of Formation

as the enthalpy change for the reaction

in which a compound is made from its

constituent elements in their elemental

forms.

Thermochemistry

• Hof .

• Standard conditions (standard state): 1 atm and 25 oC

(298 K).

• Standard enthalpy, Ho, is the enthalpy measured when

everything is in its standard state.

• Standard enthalpy of formation: 1 mol of compound is

formed from substances in their standard states.

• If there is more than one state for a substance under

standard conditions, the more stable one is used.

• Standard enthalpy of formation of the most

stable form of an element is zero.

Thermochemistry

Enthalpies of Formation

Thermochemistry

CONVENTIONAL DEFINITIONS OF

STANDARD STATES FOR

ELEMENTS

• Is the form in which the element exist

under conditions of 1 atm and 25 C.

• For O2 is gas.

• For Na is solid

• For Hg is liquid

• For C is graphite

• By definition the H of formation of the

most stable form of an element is zero.Thermochemistry

Examples – write formation reactions for each:

1. H2SO4

2. C2H5OH

3. NH4NO3

Thermochemistry

Examples

Use the tables in the back of your book to calculate

ΔH for the following reactions:

1. 4 CuO (s) 2 Cu2O (s) + O2 (g)

2. C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

3. NH3 (g) + HCl (g) NH4Cl (s)

Thermochemistry

Using Enthalpies of Formation of Calculate

Enthalpies of Reaction

• We use Hess’ Law to calculate enthalpies of a reaction

from enthalpies of formation.

Thermochemistry

Using Enthalpies of Formation of Calculate

Enthalpies of Reaction

• For a reaction

Thermochemistry

Calculation of H

H = n Hf(products)

- m Hf(reactants)

coefficients.

Thermochemistry

Calculation of H

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

• Imagine this as occurring

in 3 steps:

3 C(graphite) + 3 O2 (g) 3 CO2 (g)

4 H2 (g) + 2 O2 (g) 4 H2O (l)

Thermochemistry

Calculation of H

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

• Imagine this as occurring

in 3 steps:

3 C(graphite) + 3 O2 (g) 3 CO2 (g)

4 H2 (g) + 2 O2 (g) 4 H2O (l)

Thermochemistry

Calculation of H

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

• Imagine this as occurring

in 3 steps:

3 C(graphite) + 3 O2 (g) 3 CO2 (g)

4 H2 (g) + 2 O2 (g) 4 H2O (l)

Thermochemistry

Calculation of H

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

• The sum of these

equations is:

3 C(graphite) + 3 O2 (g) 3 CO2 (g)

4 H2 (g) + 2 O2 (g) 4 H2O (l)

Thermochemistry

Calculation of H

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

H = [3(-393.5 kJ) + 4(-285.8 kJ)] - [1(-103.85 kJ) + 5(0 kJ)]

= [(-1180.5 kJ) + (-1143.2 kJ)] - [(-103.85 kJ) + (0 kJ)]

= (-2323.7 kJ) - (-103.85 kJ)

= -2219.9 kJ

Thermochemistry

Energy in Foods

Most of the fuel in the

food we eat comes

from carbohydrates

and fats.

Thermochemistry

Fuels

of the energy

consumed in this

country comes

from fossil fuels.

Thermochemistry

HW

TOMORROW (Lab 6 – page 25)

• Remember test on monday

• Hw for Thursday up to 5.77 odd

Thermochemistry

Example

Calculate the total energy produced from the

combustion of one gram of gasoline (assume it is pure

octane, C8H18). Compare that to the energy produced

from the combustion of one gram of ethanol (a

renewable fuel – C2H5OH)

Thermochemistry

• Hess’s law: if a reaction is carried out in a number of

steps, H for the overall reaction is the sum of H for

each individual step.

• For example:

CH4(g) + 2O2(g) CO2(g) + 2H2O(g) H = -802 kJ

2H2O(g) 2H2O(l) H = -88 kJ

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)H = -890 kJ

Thermochemistry

Note that:

H1 = H2 + H3

Thermochemistry

Foods

• Fuel value = energy released when 1 g of substance is

burned.

• 1 nutritional Calorie, 1 Cal = 1000 cal = 1 kcal.

• Energy in our bodies comes from carbohydrates and fats

(mostly).

• Intestines: carbohydrates converted into glucose:

C6H12O6 + 6O2 6CO2 + 6H2O, H = -2816 kJ

• Fats break down as follows:

2C57H110O6 + 163O2 114CO2 + 110H2O, H = -75,520 kJ

• Fats: contain more energy; are not water soluble, so are

good for energy storage.

Thermochemistry

Fuels

• In 2000 the United States consumed 1.03 1017 kJ of

fuel.

• Most from petroleum and natural gas.

• Remainder from coal, nuclear, and hydroelectric.

• Fossil fuels are not renewable.

Thermochemistry

Sources of

energy

consumed in

USA

Thermochemistry

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