Refers to the portion of universe which is under observation.
Everything else in the universe except system is called surroundings. The Universe = The System + The Surroundings.
In a system, when there is exchange of energy and matter taking place with
the surroundings, then it is called an open system.
For Example: Presence of reactants in an open beaker is an example of an open system. Closed System: A system is said to be a closed system when there is no exchange of matter ‘ but exchange of energy is possible.
For example: The presence of reactants in a closed vessel made of conducting material.
In a system, when no exchange of energy or matter takes place with the surroundings, is called isolated system.
For example: The presence of reactants in a thermoflask, or substance in an insulated closed vessel is an example of isolated system.
A system is said to be homogeneous when all the constituents present is in the same phase and is uniform throughout the system.
For example: A- mixture of two miscible liquids.
A mixture is said to be heterogeneous when it consists of two or more phases and the composition is not uniform.
For example: A mixture of insoluble solid in water. ’
The state of the system: The state of a thermodynamic system means its macroscopic or bulk properties which can be described by state variables:
Pressure (P), volume (V), temperature (T) and amount (n) etc.
They are also known as state functions.
When the operation is carried out at constant temperature, the process is said to be isothermal. For isothermal process, dT = 0 Where dT is the change in temperature.
It is a process in which no transfer of heat between system and surroundings, takes place.
When the process is carried out at constant pressure, it is said to be isobaric. i.e. dP = 0
A process when carried out at constant volume, it is known as isochoric in nature.
If a system undergoes a series of changes and finally returns to its initial state, it is said to be cyclic process.
Reversible Process: When in a process, a change is brought in such a way that the process could, at any moment, be reversed by an infinitesimal change. The change r is called reversible.
It is the sum of all the forms of energies that a system can possess.
In thermodynamics, it is denoted by AM which may change, when
— Heat passes into or out of the system
— Work is done on or by the system
— Matter enters or leaves the system.
Let us bring the change in the internal energy by doing work.
Let the initial state of the system is state A and Temp. T Internal energy = u
On doing’some mechanical work the new state is called state B and the temp. T. It is found to be
T > T
u is the internal energy after change.
∴ Δu = u – u
Internal energy of a system can be changed by the transfer of heat from the surroundings to the system without doing work.
Δu = q
Where q is the heat absorbed by the system. It can be measured in terms of temperature difference.
q is +ve when heat is transferred from the surroundings to the system. q is -ve when heat is transferred from system to surroundings.
When change of state is done both by doing work and transfer of heat.
Δu = q + w
First law of thermodynamics (Law of Conservation of Energy). It states that, energy can neither be created nor be destroyed. The energy of an isolated system is constant.
Δu = q + w.
Let us consider a cylinder which contains one mole of an ideal gas in which a frictionless piston is fitted.
For isothermal expansion of an ideal gas into vacuum W = 0
It is defined as total heat content of the system. It is equal to the sum of internal energy and pressure-volume work.
Mathematically, H = U + PV
Change in enthalpy is the heat absorbed or evolved by the system at constant pressure.
ΔH = q
For exothermic reaction (System loses energy to Surroundings),
ΔH and q both are -Ve.
For endothermic reaction (System absorbs energy from the Surroundings).
ΔH and q both are +Ve.
An extensive property is a property whose value depends on the quantity or size of matter present in the system.
For example: Mass, volume, enthalpy etc. are known as extensive property.
Intensive properties do not depend upon the size of the matter or quantity of the matter present in the system.
For example: temperature, density, pressure etc. are called intensive properties.
The increase in temperature is proportional to the heat transferred.
q = coeff. x ΔT
q = CΔT
Where, coefficient C is called the heat capacity.
C is directly proportional to the amount of substance.
C = C/n
It is the heat capacity for 1 mole of the substance.
It is defined as the quantity of heat required to raise the temperature of a substance by 1° (kelvin or Celsius).
It is defined as the heat required to raise the temperature of one unit mass of a substance by 1° (kelvin or Celsius).
q = C x m x ΔT
where m = mass of the substance
ΔT = rise in temperature.
At constant volume heat capacity = C
At constant pressure heat capacity = C
At constant volume q= CΔT = ΔU
At constant pressure q = C ΔT = ΔH
For one mole of an ideal gas
ΔH = ΔU + Δ (PV) = ΔU + Δ (RT)
ΔH = ΔU + RΔT
On substituting the values of ΔH and Δu, the equation is modified as
C ΔT = CΔT + RΔT
or C-C = R
Determination of ΔU: ΔUis measured in a special type of calorimeter, called bomb calorimeter.
Working with calorimeter. The calorimeter consists of a strong vessel called (bomb) which can withstand very high pressure. It is surrounded by a water bath to ensure that no heat is lost to the surroundings.
A known mass of the combustible substance is burnt in the pressure of pure dioxygen in the steel bomb. Heat evolved during the reaction is transferred to the water and its temperature is monitored.
Enthalpy of fusion is the heat energy or change in enthalpy when one mole of a solid at its melting point is converted into liquid state.
It is defined as the heat energy or change in enthalpy when one mole of a liquid at its boiling point changes to gaseous state.
Enthalpy of sublimation is defined as the change in heat energy or change in enthalpy when one mole of solid directly changes into gaseous state at a temperature below its melting point.
Enthalpy of formation is defined as the change in enthalpy in the formation of 1 mole of a substance from its constituting elements under standard conditions of temperature at 298K and 1 atm pressure.
It is defined as the heat energy or change in enthalpy that accompanies the combustion of 1 mole of a substance in excess of air or oxygen.
A balanced chemical equation together with the value of ΔH and the physical state of reactants and products is known as thermochemical equation.
1. The coefficients in a balanced thermochemical equation refer to the number of moles of reactants and products involved in the reaction.
The total amount of heat evolved or absorbed in a reaction is same whether the reaction takes place in one step or in number of steps.
It is not possible to determine the Lattice enthalpy of ionic compound by direct experiment. Thus, it can be calculated by following steps. The diagrams which show these steps is known as Born-Haber Cycle.
A process which can take place by itself or has a tendency to take place is called spontaneous process.
Spontaneous process need not be instantaneous. Its actual speed can vary from very slow to quite fast.
(i) Common salt dissolves in water of its own.
(ii) Carbon monoxide is oxidised to carbon dioxide of its own.
The entropy is a measure of degree of randomness or disorder of a system. Entropy of a substance is minimum in solid state while it is maximum in gaseous state.
The change in entropy in a spontaneous process is expressed as ΔS
A new thermodynamic function, the Gibbs energy or Gibbs function G, can be defined as G = H-TS
ΔG = ΔH – TΔS
Gibbs energy change = enthalpy change – temperature x entropy change ΔG gives a criteria for spontaneity at constant pressure and temperature, (i) If ΔG is negative (< 0) the process is spontaneous.
(ii) If ΔG is positive (> 0) the process is non-spontaneous.
• Free Energy Change in Reversible Reaction