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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
Vapour Dome
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.
Valid for any REVERSIBLE, ADIABATIC COMPRESSION or EXPANSION of and IDEAL GAS.
Balance Equations
Mass balance
Energy balance
A process is called reversible when its direction can be reversed at any point by an infinitesimal (differential) change in external conditions. Reversible Work
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.
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:
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
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: