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Chapter 2

The First Law of

Thermodynamics

9th Edition

Contents

2.0 Introduction

2.1 Work, heat and energy

2.2 Thermal energy

2.3 The internal energy

2.4 Expansion work

2.5 Heat transactions

2.6 Enthalpy

2.7 Adiabatic change

2.8 Standard enthalpy changes

2.9 The temperature dependence of reaction

enthalpies

Introduction

concepts of thermodynamics:

• conservation of energy,

• shows how the principle of the conservation of energy

can be used to assess the energy changes.

Thermodynamics

is the study of the transformations of energy or the

study of heat and other forms of energy involved in

chemical or physical processes.

Introduction

In Physical Chemistry, the universe is divided into two parts,

the system and its surroundings.

System Surroundings

Introduction

.

Thermodynamic System:

The substance under study in

which a change occurs is called

the thermodynamic system (or

just system).

Thermodynamic Surroundings:

Everything else in the vicinity is

called the thermodynamic

surroundings (or just the

surroundings).

Introduction

The type of the system depends on the characteristics of the boundary that

divides it from the surroundings.

Open system –

can exchange both energy and matter with the surroundings.

Closed system –

exchanges energy but NOT matter with the surroundings

Isolated system –

neither energy nor matter can be exchanged with the

surroundings

Introduction

of the boundary that divides it from the surroundings.

• Both open and closed systems can exchange energy

with their surroundings.

8

Work, heat and energy

work.

opposing force, dw = –Fdz.

because of a temperature difference between the system

and the surroundings.

internal energy is the total energy of a system.

Work, heat and energy

• When the system does work (when the piston moves out), the

energy of the system is reduced and it can do less work than before.

difference between the system and its surroundings we say that

energy has been transferred as heat.

–PDV

Work, heat and energy

Work, heat and energy

which heat, q is absorbed by the system from the

surroundings. The reaction vessel will feel cool (i.e. lowering

of the temperature of the surroundings).

which heat, q is evolved by the system to the surroundings.

The reaction vessel will feel warm (i.e. rise in temperature of

the surroundings).

Work, heat and energy

Thermal energy

energy that makes use of Thermal energy

disorderly molecular motion

called thermal motion (TM)

the hot surroundings

stimulates the molecules in

the cooler system to move

more vigorously and, hence,

increase the energy of the

system.

Thermal energy

surroundings as heat, the transfer

stimulates random motion of the atoms in

the surroundings. Transfer of energy from

the surroundings to the system makes use

of random motion (TM) in the surroundings.

orderly motion in the surroundings. For

instance, the atoms shown here may be

part of a weight that is being raised. The

ordered motion of the atoms in a falling

weight does work on the system.

State function

A State Function:

Is a property of a system whose

values depend only on the state of

a system, not on the path by

which the system has reached that

state.

State function

a state function.

It is independent of the path

taken to reach it.

State function

Present State

Cooling Heating

U depends only on the present state of the system and not on the path by which it arrived at that

state.

The internal energy of 50 g of water @ 25°C is the same whether the water is cooled from a higher

temperature to 25°C or warmed from a lower temperature to 25°C

The internal energy

molecules in the system:

current state of the system.

• Changes in molar internal energy, ∆Um, are expressed in

kilojoules per mole (kJ. mol−1)

• 1 electronvolt (1 eV) is defined as the Ek acquired when

an e- is accelerated from rest through a potential

difference of 1 V.

The internal energy

When energy is

exchanged between

the system and the

surroundings, it is

exchanged as either

heat (q) or work (w).

The internal energy

joules is;

temperature of 1 g of water by 1°C.

The internal energy

• A molecule has a certain number of motional degrees of freedom, such

as the ability to translate (the motion of its centre of mass through

space), rotate around its centre of mass, or vibrate (as its bond

lengths and angles change).

The internal energy

• A molecule has a certain number of motional degrees of freedom, such

as the ability to translate (the motion of its centre of mass through

space), rotate around its centre of mass, or vibrate (as its bond

lengths and angles change).

The internal energy

the energy associated with each of these modes

of motion.

E.g. a chemical bond might break if a lot of energy

becomes concentrated in it.

The internal energy

useful guide to the average energy associated with each

degree of freedom when the sample is at a temperature.

quadratic contribution to the energy is ½(kT). Here k is

the Boltzmann’s constant with the value k = 1.381×10-23

J.K-1.

The mean energy of the atoms free to move in three

dimensions is 3/2(kT) and the total energy of a

monoatomic perfect gas is 3/2(NkT) or 3/2(nRT)

[because N = nNA and R = NAk].

The internal energy

The ET can also make quantitative predictions about how much energy

will appear in each degree of freedom. Specifically, it states that each

quadratic degree of freedom will on average possess an energy ½kT.

determine the average Ek of a particle in a gas and show that it agrees

with the equipartition result.

3

U m (T ) U m (0) RT (monoatomic gas, translational only) (2.2)

2

Where Um (0) is the molar internal energy at T = 0, when all transitional motion has ceased

and the sole contribution to the internal energy arises from the internal structure of the

atoms.

This equation shows that the internal energy of a perfect gas increases

linearly with temperature.

The internal energy

polyatomic molecules, we take into

consideration the effect of rotation

and vibration.

A linear molecule (example, N2 and

CO2) can rotate around two axes

perpendicular to the line of the

atoms, so it has two rotational

modes of motion each contributing

a term ½kT to the internal energy.

Therefore, the mean rotational

energy is kT and the rotational

contribution to the molar internal

energy is RT.

The internal energy

3

U m (T ) U m (0) RT (monoatomic gas, translational only) (2.2)

2

By adding the translational and rotational contributions, we obtain

5

U m (T ) U m (0) RT (linear molecule, translational and rotational only) (2.3)

2

The internal energy

CH4 or H2O) can rotate around

three axes and, again, each mode

of motion contributes a term ½kT to

the internal energy.

Therefore, the mean rotational

energy is 3/2(kT) and the rotational

contribution to the molar internal

energy is 3/2(RT).

The internal energy

3

U m (T ) U m (0) RT (monoatomic gas, translational only) (2.2)

2

By adding the translational and rotational contributions, we obtain

5

U m (T ) U m (0) RT (linear molecule, translational and rotational only) (2.3)

2

temperature compared with the monoatomic gas.

Reminder

Test Dates:

Test 1: 26 August 2017

(Next week Saturday)

. The first law

HEAT WORK

lost/gained Done by/on

by system system

q w

Relationship:

DU = q + w

The first law

DU = q + w

where

w = work done on a system

q = energy transferred as heat to a system

∆U = change in internal energy

surroundings, no change in internal energy occurs.

This summary of observations is known as the first law of

thermodynamics.

States that the internal energy of an isolated system is constant.

The first law

Example

If an electric motor produced 15 kJ of energy each second as

mechanical work and lost 2 kJ as heat to the surroundings. What is the

change in the internal energy, ΔU, of the motor each second?

Solution

We need to remember the sign conventions. That is, the motor

produced 15 kJ means a (-) value and the fact that 2 kJ was lost as

heat means a (-) value. Therefore, the change in the internal energy of

the motor each second is;

DU q w

DU 2kJ 15kJ 17kJ

The first law

Example

Suppose that, when a spring was wound, 100 J of work was done on it

but 15 J escaped to the surroundings as heat. What is the change in

the internal energy, ΔU, of the spring?

Solution

We need to remember the sign conventions. That is, 100 J of work was

done on it means a (+) value and the fact that 15 J of energy escaped

the system means a (-) value. Therefore, the change in internal energy

of the spring is;

DU q w

DU 100J 15J 85J

The first law

The PV Product: (Physical Meaning)

Consider the dimensions of the PV product

PV ( pressure ) (volume)

PV volume

area dimensions of work.

It therefore, means that

PV

force

length 3

the PV product

length 2 expresses mechanical

work.

PV ( force) (length)

The first law

The work required to compress a gas

The work done by a gas when it expands

.

For the reaction

2Na(s) + 2H2O(l ) 2NaOH(aq) + H2(g)

–PDV

For the reaction as written at 1 atm, -PDV = -2.5 kJ.

In addition, 368.6 kJ of heat are evolved.

The first law

Expansion work

The work done by a gas on expansion is equal to the product of the external

pressure against which the gas is expanding multiplied by the volume change

the gas undergoes.

dw Pext dV

where:

Consider an finite change: dw = work done by the gas

Pext = external pressure

V2

dV = change in volume

w Pext dV

V1

Let us consider some cases in which the integration can be performed easily.

The first law

A gas expands isothermally into an evacuated vessel.

In this case,

dw Pext dV

dV 0

Therefore: So we can see that when

a gas expands freely into

dw 0 a vacuum, there is no

work done in the

w 0 expansion.

The first law

The external pressure remains constant during the expansion.

Therefore, from V2

w Pext dV In an expansion:

V1

V2 > V1

If we integrate, we obtain:

Therefore,

w Pext V2 V1

V2 - V1 > 0

w Pext DV w <0

The first law

of a variable.

Reversible expansion: Here the external pressure is only infinitesimally less than

the internal pressure (the pressure exerted by the gas) at any instant. Therefore,

we can write,

Pext Pint

Where Pint is the pressure of the gas.

The first law

Finding the expression for the This expression can be used to express Pint,

work done (Reversible isothermal expansion) V2

nRT

We consider the equation, w dV

V1

V R = the gas

V2 Therefore, we can write constant

w Pext dV V2 n = constant for a

1

given amount of

V1

w nRT dV gas

We write Pint instead of Pext V1

V T = constant in an

V2 isothermal

w Pint dV

By integrating, we obtain: process

V1 V2

In order to integrate, we must be able to

w nRT ln

express the pressure of the gas in terms of V1

its volume. This can be done by using the This can also be written as,

state equation of the gas. Consider the

case of an ideal gas.

P P1V1 P2V2

nRT w nRT ln 1

P P2

V

The first law

4. Adiabatic expansion

Adiabatic change: A change that occurs in a system that is isolated from its

environment, so that no heat may enter or exit the system. Therefore, in an

adiabatic change,

dq 0

Any work done by the

Equation,

system during an

dU dq dw

adiabatic change is done

then becomes, at the expenses of the

dU dw internal energy

The first law

Example

Calculate the work done when 50.00 g of iron dissolves in hydrochloric acid

at 25°C:

a) In a closed vessel Useful Data:

b) In an open beaker Mass of iron that reacts =

50.00 g

Temperature: 25°C=298

Solution:

K

Mm Fe = 55.85 g.mol-1

Write a balanced chemical equation for the reaction:

The vessel is closed: therefore, no expansion work is possible, and the volume

does not change. This means DV 0

and consequently,

w 0

The first law

Since the beaker is open, the gas produced in the reaction expands against

constant pressure of the atmosphere. We use equation:

w PDV

Consider that the initial volume of the reactants is negligible in comparison with the

volume of the gas formed. Therefore, we can write;

DV VH 2

Where VH2 is the volume of hydrogen gas formed in the reaction.

The expression for the work done becomes;

w P VH 2

Assume that hydrogen is an ideal gas, and write the state equation for it

P VH 2 nH 2 RT

The first law

w nH 2 RT

Find number of moles of hydrogen gas;

50.00 g

nFe 1

0.90mol

55.85 g.mol

nH 2 0.90mol

w nH 2 RT

w 0.90mol 8.314 J .K 1mol 1 298 K

w 2.22 103 J

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