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4 UNIVERSAL LAWS THAT CANT BE BROKEN

0th law - defines temperature (T) If hot object is placed in thermal contact with a cold object, heat flows from the warmer to the cooler object. This continues until thermal equilibrium is reached whereby the heat stops flowing. At this point both objects have the same temperature. Formally - If body A and body B are in thermal equilibrium and body B and body C are in thermal equilibrium, then A and C are in thermal equilibrium. This is the principle of the thermometer. 1st law - defines energy (U) When a system changes from one state to another along an adiabatic path, the amount of work done is the same irrespective of the means employed.

enthalpy 2nd law - defines entropy (S) Uses entropy S (state function) to identify the spontaneous (irreversible) changes amongst those permissible changes.

3rd law - gives numerical value to entropy System - The material in the portion of space we are interested in , e.g. reaction vessel, engine, turbine e.t.c.

Definitions
Surroundings - Rest of the universe, environment. Boundary - Separation between system and surroundings. Open System - Matter can be transferred between system and surroundings. Closed System - Matter CAN NOT be transferred between system and surroundings Adiabatic Process A process during which no heat transfer to/from the surroundings occurs Isothermal Process A process by during which heat transfer to the surroundings occurs causing the temperature to remain constant

2 types of properties

Extensive - scales with the size of the system e.g. mass, volume Intensive - independent of system size e.g. temperature, pressure. Turning extensive properties into intensive ones

Work

Heat capacity

Molar heat capacity

PVT Properties of Pure Gases and Liquids


2D p-v-T diagram

Vapour Dome

The Energy Balance

3 types of energy considered, K. E., P. E. and internal energy.

Piston - Cylinder Apparatus Ideal gas in reversible process

N.B. this expression is only valid for P = Pb, T = constant and the fluid is an ideal gas. Enthalpy The sum U + PV is a property of the incoming mass called ENTHALPY, H.

Heat capacity No work done, closed system, constant volume

Heat capacity at constant volume

With polynomial form

Heat capacity at constant pressure

For ideal gases:

Work for adiabatic reversible compression

Valid for any REVERSIBLE, ADIABATIC COMPRESSION or EXPANSION of and IDEAL GAS.

Balance Equations
Mass balance

Energy balance

Joule Thomson expansion

Reversible and Irreversible Processes


This type of process is called IRREVERSIBLE because we cannot recover the energy that has been dissipated. In general the more quickly a process happens the more irreversible it is.

A process is called reversible when its direction can be reversed at any point by an infinitesimal (differential) change in external conditions. Reversible Work

Joule Thomson expansion

Second law Second Law Puts restrictions on useful conversion of q to w. Follows observation of a directionality to spontaneous processes. Provides a set of principles for: Determining the direction of a spontaneous change. Determining equilibrium state of system.

The carnot cycle

Efficiency

Efficiency

q1 q2 q 1 2 q1 q1

q2 T 1 2 q1 T1

Third law

dS

dqrev dq S S2 S1 rev T T 1

For isolated systems S > 0 For a spontaneous, irreversible process. S = 0 For a reversible process. S < 0 Impossible Calculating entropy changes For an isothermally expanding ideal gas:

Equilibrium and free energy Fundamental equations

dH = TdS + Vdp Equilibrium is achieved when entropy is maximized. At maximum entropy no spontaneous changes can occur. Hemholtz Free Energy A = U TS

Is the criteria for spontaneity under these conditions. Gibbs free energy G = U + pV TS

Clayperon equation

The Clapeyron equation tells us how the boiling or melting point changes with pressure Clausius clayperon equation

Thus we plot a graph of ln p vs 1/T versus we can work out the enthalpy of vapourization from the gradient. Reaction equilibria

Rate constants

Using gibbs free energy of formation

Examine

This expression can be integrated between the initial number of moles of species i, nio and the final number ni and the initial extent of reaction, which is zero and leading to: