# 8 Chemical

thermodynamics

**8.1 Introduction to chemical thermodynamics
**

Chemical thermodynamics allows us to predict both the direction and the extent of spontaneous chemical and physical change under particular conditions using a property called the Gibbs free energy, G.

**8.2 Gibbs free energy
**

Chemical reactions and physical changes almost always either absorb or release energy as heat. Energy may be distributed throughout a chemical system in a large number of different ways, some of which have significantly higher probabilities than others

**8.2 Gibbs free energy
**

G = H ± TS H enthalpy of the system

± Function related to the heat absorbed or evolved by a chemical system

** S entropy of the system
**

± Measure of number of ways energy is distributed throughout a chemical system

T temperature in kelvin

**8.2 Gibbs free energy
**

G= H±T S G allows us to determine whether a particular chemical reaction or physical change is spontaneous If G < 0, the process is spontaneous If G > 0, the process is nonspontaneous If G = 0, the system is at equilibrium

**8.2 Gibbs free energy
**

System refers to the particular chemical species being studied Surroundings are everything else

**8.2 Gibbs free energy
**

Universe refers to the system and the surroundings Boundary defined as region across which heat flows

**8.2 Gibbs free energy
**

Open systems

± Can gain or lose mass and energy across their boundaries

Closed systems

± Can absorb or release energy, but not mass, across the boundary

Isolated systems

± Can not exchange matter or energy with their surroundings

**8.2 Gibbs free energy
**

SI unit of energy

± Joule ± 1 J = 1 kg m2 s-2 ± 1 kJ = 103 J

** Thermodynamic equations require the temperature in kelvin
**

± Temperature difference ( T) of 1 K is numerically equal to T of 1 °C

8.3 Enthalpy

Internal energy (U)

± The sum of energies for all of the individual particles in a sample of matter ± Interested in the CHANGE in internal energy that accompanies a process U = Ufinal ± Uinitial U = Uproducts ± Ureactants

8.3 Enthalpy

Internal energy

± Chemical system can exchange energy with its surroundings in two ways ± Either absorbing heat from or emitting heat to the surroundings ± Doing work on the surroundings of having the surroundings do work on it ± Work may be defined simply as motion against an opposing force

8.3 Enthalpy

Internal energy

± Type of work most often encountered in chemical systems is the compression or expansion of gas ± Often called pressurevolume or pV work ± w = ±p V

8.3 Enthalpy

First law of thermodynamic U=q+w

± q - heat ± w - work ± Energy can be transferred between systems as either heat or work ± It can never be created or destroyed ± Law of conservation of energy

8.3 Enthalpy

State functions

± Value is dependent only on the current state of the system ± X = Xfinal ± Xinitial ± Independence from the method or mechanism by which a change occurs is the important feature of all state functions

8.3 Enthalpy

State functions

± q and w are NOT state functions ± The values of q and w are dependent on the path of change

8.3 Enthalpy

Heat Capacity

± Heat and temperature are not the same thing ± Heat is a transfer of energy due to a temperature difference q=C T ± q - heat (J) ± C - heat capacity (J K-1)

8.3 Enthalpy

Heat Capacity

± Heat capacity depends on the size of the sample ± A property with a value that depends on the size of the sample is an extensive property ± A property with a value independent of the size of the sample is an intensive property

8.3 Enthalpy

Heat Capacity

± Divide heat capacity (extensive property) by the mass of the sample to form specific heat capacity (intensive property)

C c ! m

± c - specific heat capacity (J g-1 K-1) ± Divide by amount instead of mass to form molar heat capacity (J mol-1 K-1)

8.3 Enthalpy

Heat Capacity q=c T

If a gold ring with a mass of 5.50 g changes in temperature from 25.0 to 28.0 °C, how much heat has it absorbed? m = 5.50 g c = 0.129 J g±1 K±1 T = 3 K q = cm T = (0.129 J g-1 K-1) × (5.50 g) × (3 K) = 2.1 J

8.3 Enthalpy

The determination of heat

± Calorimeter

Apparatus designed to minimise heat loss between the system and surroundings

± Bomb calorimeter

System remains at constant volume U=q+w U = qv

8.3 Enthalpy

Enthalpy: the heat of reaction at constant pressure

U=q+w U = qp ± p V ± Inconvenient as need to know V ± Define a new thermodynamic property called enthalpy (H) H = qp

8.3 Enthalpy

Enthalpy: the heat of reaction at constant pressure

H = U + pV H= U+p V ± Substituting U = qp ± p V gives H = qp ± p V + p V H = qp

8.3 Enthalpy

Enthalpy: the heat of reaction at constant pressure

± The heat of reaction at constant pressure is equal to H ± The heat of reaction at constant volume is equal to U ± H > 0 reaction is endothermic ± H < 0 reaction is exothermic ± The difference between H and U for a reaction is p V

8.3 Enthalpy

Standard enthalpy change

± Standard states

Pressure of 105 Pa Concentration of 1 M

**± Standard enthalpy of reaction
**

Value of H for a reaction occurring under standard conditions ( H (kJ or kJ mol±1) Involves the actual numbers of MOLES specified by the coefficients of the equation

8.3 Enthalpy

Standard enthalpy change

N2(g) + 3H2(g) 2NH3(g) H = ±92.38 kJ ± The above is a thermochemical equation ± Always gives the physical states of the reactants and products ± Its value of H is only true when coefficients of reactants and products are numerically equal to the number of moles of the corresponding substances

8.3 Enthalpy

Hess¶s law

± Method for combining known thermochemical equations in a way that allows us to calculate H for another reaction ± One step

C(s) + O2(g) CO2(g) H = ±393.5 kJ CO(g) H = ± 110.5 kJ CO2(g) H = ± 283.0 kJ

± Two step

Step 1: C(s) + ½O2(g) Step 2: CO(g) + ½O2(g)

8.3 Enthalpy

Hess¶s law

2Fe(s) + 3CO2(g) 3CO(g) + O2(g) 2Fe(s) + O2(g) Fe2O3(s) + 3CO(g) 3CO2(g) Fe2O3(s) H = +26.7 kJ H = -849.0 kJ H = -822.3 kJ

**± Rules for manipulating thermochemical equations: 1. When an equation is reversed the sign of H must also be reversed.
**

Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g) 2Fe(s) + 3CO2(g) H = -26.7 kJ Fe2O3(s) + 3CO(g) H = +26.7 kJ

8.3 Enthalpy

Hess¶s law

2Fe(s) + 3CO2(g) 3CO(g) + O2(g) 2Fe(s) + O2(g) Fe2O3(s) + 3CO(g) 3CO2(g) Fe2O3(s) H = +26.7 kJ H = -849.0 kJ H = -822.3 kJ

± Rules for manipulating thermochemical equations: 2. Formulae can be cancelled from both sides of an equation only if the substance is an identical physical state.

8.3 Enthalpy

Hess¶s law

2Fe(s) + 3CO2(g) 3CO(g) + O2(g) 2Fe(s) + O2(g) Fe2O3(s) + 3CO(g) 3CO2(g) Fe2O3(s) H = +26.7 kJ H = -849.0 kJ H = -822.3 kJ

± Rules for manipulating thermochemical equations: 3. If all the coefficients of an equation are multiplied or divided by the same factor, the value of H must likewise be multiplied or divided by that factor.

CO(g) + ½O2(g) 3CO(g) + 3/2O2(g) CO2(g) 3CO2(g) H = -283.0 kJ H = -849.0 kJ

8.3 Enthalpy

Standard enthalpy of combustion

± cH ± Enthalpy change at temperature T when 1 mole of a substance is completely burned in pure oxygen gas ± Combustion reactions are always exothermic ± cH always negative ± kJ mol±1

8.3 Enthalpy

Standard enthalpy of formation ( fH )

± Enthalpy change when 1 mole of substance is formed at 105 Pa and the specified temperature from its elements in their standard states ± An element is in its standard state when it is in its most stable form and physical state at 105 Pa and the specified temperature ± fH for the elements in their standard states are 0

8.3 Enthalpy

Standard enthalpy of formation

aA + bB cC + dD U U U U (H U ! c (f HC d (f H D «a (f H A b (f H B » ½ ± Hess¶s law equation ± Use either enthalpies of combustion or enthalpies of formation

8.3 Enthalpy

Bond enthalpies

± A bond enthalpy is the enthalpy change on breaking 1 mole of a particular chemical bond to give electrically neutral fragments ± Atomisation enthalpy ( atH) is the enthalpy change that occurs on rupturing all the chemical bonds in 1 mole of gaseous molecules

8.3 Enthalpy

Bond enthalpies and Hess¶s law

8.3 Enthalpy

Lattice enthalpies and Hess¶s law

± Lattice enthalpies for ionic solids calculable using Hess¶s law and thermodynamic data

8.4 Entropy

Entropy and probability

No energy is transferred Two units of energy are transferred Three units of energy are transferred

One unit of energy is transferred

± Spontaneous processes tend to proceed from states of low probability to states of higher probability. ± Spontaneous processes tend to disperse energy

8.4 Entropy

Entropy and entropy change

± Entropy (S) describes the number of equivalent ways that energy can be distributed in the system ± Entropy is a state function S = Sproducts ± Sreactants ± Any event that is accompanied by an increase in the entropy of the system has a tendency to occur spontaneously

8.4 Entropy

Entropy and entropy change

8.4 Entropy

Factors that affect entropy

± Often possible to predict whether S is positive or negative for a particular change ± Volume

For gases the entropy increases with increasing volume

8.4 Entropy

Factors that affect entropy

± Temperature

The higher the temperature the higher the entropy

8.4 Entropy

Factors that affect entropy

± Physical state

One of the major factors that affects the entropy of a system is its physical state

8.4 Entropy

Factors that affect entropy

± Number of particles

When all other things are equal, reactions that increase the number of particles in the system tend to have a positive entropy change

8.4 Entropy

The second law of thermodynamics

± Whenever a spontaneous event takes place in our universe, the total entropy of the universe increases ( Stotal>0) ± Stotal = Ssystem + Ssurroundings

(Ssurroundings ! q suroundings T

**± qsurroundings = -qsystem ± qsystem = H
**

(Ssurr undin s ! T

(H system

8.4 Entropy

Absolute entropy and the third law of thermodynamics

± At absolute zero, the entropy of a perfectly ordered pure crystalline substance is 0 S = 0 at T = 0 K ± Point at which entropy equal to 0 is known, hence by experimental measurement and calculation entropy can be determined for a substance at temperatures above 0 K

8.4 Entropy

Absolute entropy and the third law of thermodynamics

± Standard entropy (S ) ± entropy of 1 mole of a substance determined under standard conditions at temperature of 298 K ± Standard entropy of reaction aA + bB cC + dD

U U U U (S U ! c (f SC d (f SD «a (f S A b (f SB » ½

**8.5 Gibbs free energy and reaction spontaneity
**

The sign of G

G = H ±T S G < 0 reaction spontaneous

**8.5 Gibbs free energy and reaction spontaneity
**

Standard Gibbs free energy change

± When G is determined at 105 Pa, this is called the standard free energy change ( G) ± There are several ways for determining G for a reaction

G = H ±T S aA + bB cC + dD

U U U U (G U ! c (f GC d (f GD «a (f G A b (f GB » ½

**8.5 Gibbs free energy and reaction spontaneity
**

Gibbs free energy and work

± Maximum conversion of chemical energy to work occurs if a reaction is carried out under conditions that are said to be thermodynamically reversible

**8.5 Gibbs free energy and reaction spontaneity
**

Gibbs free energy and work

± The maximum amount of energy produced by a reaction that can be THEORETICALLY harnessed as work is equal to G ± G = 0 the system is in a state of equilibrium Gproducts = Greactants ± When G = 0 the amount of work available is 0

**8.5 Gibbs free energy and reaction spontaneity
**

Gibbs free energy and work

± For phase changes such as H2O(l) H2O(s) equilibrium can be established only at one particular temperature at atmospheric pressure G=0= H±T S H=T S

(H (S ! T (H T ! (S

**8.5 Gibbs free energy and reaction spontaneity
**

Gibbs free energy and work