Thermodynamics

Thermodynamics literally speaking means flow of heat and deals with the quantitative relationship between heat and other forms of energy in physio-chemical transformations. It is sometimes called energetics. The subject matter of thermodynamics is based on three fundamental laws. They are applicable to all the phenomena in nature. These laws are not based on any theory but are based on experimental facts. The laws have been subjected to rigorous mathematical treatment and have yielded correlations between different observable properties of matter. These have been proved to be very convenient and useful in describing the states of system in chemical and physical transformations. The result of thermodynamic deductions have been proved to be correct by experiments and found to be rigidly valid. Thermodynamics is, therefore an exact science. Thermodynamics has a great predicting power. It can predict whether a given process will occur spontaneously or not under a given set of conditions. The laws provide necessary criteria for predicting the feasibility of a process. However it gives no information with regard to the rate at which a given change will proceed. Thermodynamics deals only with the states of the system and makes no mention of the mechanism of ho the change is accomplished.Thermodynamics answers to why a change occurs but not to how it occurs. Classical thermodynamics is based on the behaviour of bulk or macroscopic properties of the system, i.e, systems having many molecules and is independent of the atomic and molecular structure. Consequently, no information can be obtained regarding the molecular structure. This difficulty is however obviated in statistical thermodynamics where the laws of mechanics are applied to the behaviour of individual molecules and then a suitable average is taken. The results obtained from classical and statistical thermodynamics are however complementary to each other.

ChemistryPhysical ChemistryThermodynamicsLaws of Thermodynamics

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Laws of Thermodynamics
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Introduction to the three Laws of Thermodynamics

1. The three Laws of Thermodynami cs : Zeroth Law of Thermodynami cs

Thermodynamics is a branch of physics which deals with the relation between heat and mechanical energy and its related phenomenon. In earlier days heat was considered as a fluid called caloric which is supposed to be weight-less and that is present in every body. Later on Count Rumford in 1798 found that a large amount of heat was produced by friction and the heat produced by friction was proportional to the work done. Sir Humphrey Davy in 2. The three Laws his experiment rubbed two blocks of ice in vacuum and found of melted due to friction, which disagrees with the idea of caloric as Thermodynami there is no other hot body in surroundings for the fluid to transfer. cs : first Law of We observe here generation of heat, when the mechanical work is Thermodynami done on the body. The same heat is also generated whe the ice cs blocks are directly heated. Thus we understand that heat and work 3. The three Laws are both forms of energy. James Joule and others later on showed that heat lost or gained in any process could be accounted for an of Thermodynami equal amount of work done by the system or on the system. This cs : Second Law idea lead to extend the concept of energy to include heat as a form of of energy, to apply the law of conservation of energy. We have 3 Thermodynami laws of thermodynamics.

cs

1. Zeroth law of thermodynamics 2. First law of thermodynamics 3. Second law of thermodynamics

The three Laws of Thermodynamics : Zeroth Law of Thermodynamics

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Let us consider two systems A and B separated from each other by thermally insulated wall (one that conducts no heat), but each being in contact of a third system C through a (diathermic) wall which permits heat to pass. Then the system A will be in thermal equilibrium with system C and similarly system B will also be in thermal equilibrium with system C. Now if the adiabatic wall between systems A and B is replaced by a diathermic wall, experiments show that no further change occurs in a system A and B indicating thereby the system A was also in thermal equilibrium with B. This important experimental fact leads to the following general conclusion. " If two systems are in thermal equilibrium with a third system then they must be in thermal equilibrium with each other' . This statement is called the zeroth law of thermodynamics and forms the basis of concept of temperature. All these three systems can be said to possess a property that ensure their being in thermal equilibrium with one another. This property is known as temperature. We may, therefore define the temperature of a system as a property that determines whether or not the system is in thermal equilibrium with the neighbouring systems. It is obvious that if two systems are not in thermal equilibrium, they will be at different temperatures. The law was formulated by R.H.Fowler in 1931. It is formulated long after the first and second laws of thermodynamics. Since it is more fundamental in concept than the other two it is named as 'Zeroth law'.

The three Laws of Thermodynamics : first Law of Thermodynamics

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Let in a process, an amount dQ of heat be given to the ideal gas and an amount dW of work be done by it. The total energy of the gas increases by (dQ - dW) . As a result, the internal energy (random motion of the molecules) of the gas may increase. If dU is the change in internal energy, we have

dQ = dU + dW. This equation is the statement of the 'first law of thermodynamics'. In an ideal monoatomic gas, the internal energy of the gas is simply translational energy of all the molecules. In general, the internal energy may get contribution from the vibrational kinetic energy of molecules, rotational kinetic energy of molecules as well as from the potential energy corresponding to the molecular forces. The above equation hence represents a statement of conservation of energy as applicable to any thermodynamic system however complicated. It should be remembered that when work is done by the system, dW is positive. If work is done on the system dW is negative. When heat is given to the system or heat is absorbed,dQ is positive, If heat is given by the system or heat is evolved, dQ is negative. If zeroth law defines a property of matter called temperature, teh first law enables us to define a property of a system called internal energy. We can write the above equation as dU = dQ - dW. In the case of an isolated system, there is no interaction with the surroundings. No work is doe by or on the system, i.e., dQ = 0 and dW = 0 dU = 0 or U = constant i.e., the internal energy of an isolated system is constant. When the heat supplied is completely converted into work without changing the temperature of the system, the internal energy of the system remains constant i.e., dU = 0. :. dQ = dW

The three Laws of Thermodynamics : Second Law of Thermodynamics

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First law of thermodynamics conveys the basic idea of conservation of energy in the thermodynamic system. It relates heat energy and mechanical work. It considers heat as a form of energy (internal energy) to generalize the law of conservation of energy. To explain the lack of reversibility in nature, second law of thermodynamics is formulated. It was first announced by Clausius as follows: Clausius Statement " It is impossible for a self acting machine unaided by any external agency of transfer heat from a body at lower temperature to a body at higher temperature" This statement indicates the direction of flow of heat. It can also be stated as heat on its own can not flow from a cold body to a hot body. Kelvin Statement " It is impossible by any thermodynamic process which results solely in the removal of heat from a heat reservoir and convert it entirely into work." The statement can be interpreted as no heat engine can convert whole of the heat energy supplied to it into useful work.

Properties of Thermodynamic System

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Here in this page we are going to discuss about properties of thermodynamic system concept.
Thermodynamics literally means flow of heat and deals with the quantitative relationship between heat and other forms of energy in physio-chemical transformations. The subject matter of thermodynamics is based on three fundamental laws. They are applicable to the entire phenomenon in nature. These laws are not based on any theory but are based on experimental facts. The laws have been subjected to rigorous observable properties of matter. Thermodynamics can predict whether a given process will occur spontaneously or not under a given set of conditions. The laws provide necessary criteria for predicting the feasibility of a process; however it gives no information with regard to the rate at which a given change will proceed. Thermodynamics deals only with state of the system and makes no mention of the mechanism of how the change is accomplished and it will provide answer to why a change occurs but not how it occurs.

1. Properties of a System

Properties of a System
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Measurable properties of a system may be divided into two classes;

1. Extensive and
2. Intensive

Extensive property
An extensive property of a system depends upon the total amount of material in the system. Mass, volume, internal energy, heat contents, free energy, entropy, and heat capacity are all extensive properties.

Mass: This gives the idea of how much of the initial matter was contained in the system and how much is left after the process is complete. Volume: This gives an idea of the dimension of the matter contained in and what will be the final dimension after the process is over. Internal energy: It is the total energy contained in to create the thermodynamic system but excludes the energy to displace the systems surroundings. It has two major components of kinetic energy and

potential energy due to the movement of particles and the static electric energy of the atoms contained in.

Heat contents: Under a given pressure, the heat content or Enthalpy is a measure of total energy of a thermodynamic system. It includes internal energy which is required to create a system and establish its volume and pressure.

Free energy: It is the energy in the physical system which can be converted into work. Entropy: It is a thermodynamic property which is used to determine the energy available for useful work in a thermodynamic process. Heat capacity: Heat capacity or thermal capacity is the measurable physical quantity that gives an idea of the amount of heat required to change a substances temperature by a given range.

Intensive property
An intensive property is defined as a property which is independent of the amount of material in the system. Density, molar property, surface tension, viscosity, specific heat, thermal conductivity, refractive index, pressure, temperature, boiling point, freezing point, and vapour pressure of a liquid are all intensive properties.

Density: Density of a material is defined as a ratio between its volume and the matter contained in or mass. Molar property: Molar property mainly consists the detailing of molar volume, molar energy, molar entropy, molar heat capacity and all these are quantified from the point of moles of the substance involved in.

Surface tension: It is a property of a liquid surface which helps in resisting any kind of external force applied on it. Viscosity: It is a measurable internal quantity of a fluid which resists its flow. Specific heat: It is the amount of heat per unit mass required to raise the temperature by one degree Celsius. Thermal conductivity: Thermal conductivity () is the intrinsic property of a material which relates its ability to conduct heat. Refractive index: The measure of the speed of light in a medium is referred as refractive index of that medium. Pressure: It is the perpendicular force acting per unit area on the surface of an object. Temperature: It is the property of the matter which quantitatively expresses the coldness or hotness of substance. Boiling point: It is the temperature of the substance at which the vapour pressure of the liquid equals environmental pressure. Freezing point: It is the temperature at which a liquid composition solidifies under a given pressure. Vapour pressure of a liquid: It is defined as the equilibrium pressure above its liquid resulting due to the evaporation of liquid.

Thermodynamic system depending upon interactions between system and surroundings can be classified as open systems, closed systems and isolated systems.

1. Open systems: A system which can exchange both matter and energy with the surroundings.

2. Closed system: A System in which the exchanges of energy with the surroundings is possible, and
while the transfer of matter to and from the surroundings does not take place.

3. Isolated system: It is a system that prevents any interactions between the system and the
surroundings.

ChemistryPhysical ChemistryThermodynamicsProperties of Thermodynamic SystemEnthalpy

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Enthalpy
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1. Enthalpy Change 2. Origin of Enthalpy Change in a Reaction 3. Relationship between Dh and de

Here in this page we are going to discuss about chemistry concept called enthalpy.The change in internal energy gives the heat change accompanying a chemical reaction at constant volume. However, most of the chemical reactions carried out in laboratories, are open to normal atmospheric conditions. A chemical reaction in a laboratory may incur change in volume but the pressure remains constant i.e. atmospheric pressure. To study the heat changes for reactions at constant pressure and at constant temperature, a new term called enthalpy has been introduced. The enthalpy of a system may be defined as the sum of the internal energy and the product of its pressure and volume. It is denoted by the symbol H and is given by H = E + PV where, E = internal energy, P = pressure and V = the volume of the system. Enthalpy is also called heat content.

Enthalpy Change
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Every substance has a definite value of enthalpy in a particular state. Like internal energy, the absolute value of enthalpy cannot be measured. However, the change in enthalpy accompanying a process can be determined as the difference between the enthalpies of the products and the reactants, i.e., DH = Hproducts - Hreactants = Hp - Hr where, 'Hp' is the enthalpy of the products, 'Hr' is the enthalpy of the reactants and DH is the enthalpy change. If a reaction is carried out at constant temperature and pressure the heat exchanged (evolved or absorbed) by the system with the surroundings (i.e., heat change - DH) is equal to change in enthalpy.

Origin of Enthalpy Change in a Reaction

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We know that in chemical reactions, energy is required to break old bonds of the reactants. Energy is also released to form new bonds, which give the end products. The net energy change (released or absorbed) in a reaction will be equal to energy required to break all the bonds in reactants minus the energy released during the formation of bonds in the products.

If energy required is greater than energy released, the net result will be the absorption of energy and the reaction will be endothermic, i.e. DH = + ve. If energy released is greater than energy required, the net result is the release of energy and the reaction will be exothermic (DH = - ve). This can be illustrated by considering a chemical reaction between hydrogen gas and chlorine gas to form hydrochloric acid gas:

The energy required in breaking one mole of bonds in hydrogen and chlorine molecules are 437 and 244 kJ respectively.

It is observed that for the formation of one mole of HCl, 433 kJ of energy is released. Therefore, the energy released during the formation of 2 moles of HCl is 2 x 433 = 866 kJ.

Thus, Enthalpy change = (437+244) - (2 x 433) = -185 kJ

DH = - 185kJ Therefore, 185 kJ of energy is released during the formation of 2 moles of gaseous HCl from one mole each of gaseous hydrogen and gaseous chlorine. The amount of heat exchanged with the surroundings for a reaction at constant pressure (DH) is different from that exchanged at constant volume (DE) and temperature. The energy changes for reactions at constant pressure, includes energy contributions due to expansion or contraction against atmospheric pressure i.e. the volume of the reacting system changes. If the volume increases, the system expands against the atmospheric pressure and energy is required for this expansion. Therefore, a part of energy will be used for the expansion. Thus the amount of heat exchanged at constant pressure (DH) would be less than the amount of heat exchanged at constant volume (DE).

Alternatively, if the system contracts at constant pressure, work is done on the system and the system absorbs some energy from the surroundings. Therefore, the amount of heat exchanged at constant pressure is greater than that exchanged at constant volume.

Relationship between Dh and de

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Consider a reaction

at constant pressure 'P'. Let HA be the enthalpy of the reactants and HB be the enthalpy of products so that change in enthalpy, DH may be DH = HB - HA But H = E + PV. Let EA and VA be the internal energy and volume of the reactants and EB and VB corresponding values for the products. Therefore, HA = EA + PVA and HB = EB + PVB DH = (EB + PVB) - (EA + PVA) or DH = (EB - EA) + P(VB - VA) or DH = E+ PDV where DE is the change in internal energy and DV is the change in volume of the system.

Enthalpy Heat Capacity Gibbs Free Energy

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Heat Capacity

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Heat capacity gives a measure of the quantity of heat absorbed by a system. It is defined as the amount of heat required to rise the temperature of the system through 1oC. If the quantity of heat 1. Significance of required is to raise the temperature of unit mass of the substance C through 1oC then it the specific heat of the substance. Whereas 2. Molar Heat when the whole mass of the substance is considered, it is the heat Capacities capacity.
3. Relationship between C 4. The Ratio C 5. Calculate Heat Capacity

If 'q' is the heat required by the system to raise its temperature from T1 to T2, mathematically the heat capacity C of the system is given by the expression:

The value of 'C' is considered over a small temperature range as heat capacity varies with temperature. If dq is the heat required to raise the temperature of the system from T to T + dT, then

Heat capacity is a path function and so the conditions such as constant volume or constant pressure have to be specified to define the path for calculating the heat capacity of a system. The heat capacity at constant volume is represented by Cv and that at constant pressure is represented by Cp.

Significance of C
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and Cp

For infinitesimally small changes, the expression for the first law can be written as dE = dq + dw = dq - PdV

or dq(v) = dE

dH = dE + PdV or

Substituting in (i) d q(p) = dH - PdV + PdV = dH

Thus, heat capacity at constant volume represents the rate of increase of internal energy of the system with temperature, while the heat capacity at constant pressure represents the rate of increase of enthalpy of the system with temperature.

Molar Heat Capacities

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The heat capacities of 1 mole of a gaseous system at constant volume and at constant pressure are called molar heat capacities.

Relationship between C
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and Cv

When the temperature of 1 mol of ideal gas is to be raised through one degree (1 K) the gas is heated at constant volume. The gas under this condition does no external work and the heat supplied increases the internal energy of the gas. When the gas is heated at constant pressure, there will be an increase in its volume. The gas will expand and do some external work. Extra heat must be supplied to the gas to enable it to perform this external work. Thus, heat capacity at constant pressure (Cp) is larger than that at constant volume (Cv). The difference between the two i.e., (Cp - Cv), gives the work done by 1 mol of the gas in expansion when it is heated through one degree. This represents the work done per mol per degree rise in temperature, i.e., R the universal gas constant. Thus, Cp - Cv = R The above conclusion can be arrived mathematically as follows:

Also H = E + PV For an ideal gas, PV = RT Therefore H = E + RT

Comparing (i) and (ii) Cp - Cv = R For 1 mol of ideal gas The above relation is also called Meyer's relationship. It can also be written as Cp - Cv = R = 1.99 cal K-1 mol1

=8.314 JK-1 mol-1.

The Ratio C
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/Cv

The ratio of molar heat capacities at constant pressure to that at constant volume is represented by g . The value of g gives information about the atomicity of gases

For monoatomic gases g = 1.67 For diatomic gases g = 1.40 For triatomic gases g = 1.30

Calculate Heat Capacity

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Problem: A gas expands from a volume of 3.0 dm3 to 5.0 dm3 against constant external pressure of 3.0 atm. The work of expansion is used to heat 10.0 mol of water at temperature 290.0 K. Calculate final temperature of water. (Specific heat of water = 4.184 JK-1 g-1) Solution: W = - P (V2 - V1) = -3 x (5 - 3) = -6L.atm.= -6 x 101.25 J = 6.07 x 102 J Now, Q = m. C.DT

Final temperature

Gibbs Free Energy Change and Work

We have learnt that of DG is a measure of the spontaneity of a chemical reaction. It can be shown that the free energy of a process is equal to maximum possible work that can be derived from the process as given below:

Sub Topics

1. Free Energy Change and Electrical Work From first law of thermodynamics, it is known that DE = q + w, done in a Cell where q is the heat absorbed by the system,DE is the change in

internal energy and w is the work done on the system. The work

may be expansion work as well as non-expansion work. The nonexpansion work can be used for useful effects; For e.g., electrical work. This is also called non-pressure-volume work or useful work. The work due to expansion at constant temperature known as pressure volume work is given by - PDV. Thus, DE = q + wexpansion + wnon-expansion ......(4) = q - PDV + wnon-expansion or = DE - PDV + wnon-expansion Now, DE + PDV = DH or q = DH - wnon-expansion .....(5) For a process carried out reversibly at constant temperature, DS = qrev / T or qrev = TDS Substituting in Equation 5, TDS = DH - wnon-expansion DH - TDS = wnon-expansion DH - TDS = DG so that DG = wnon-expansion or - DG = - wnon-expansion The non-expansion work may be regarded as useful work. Thus, the decrease in free energy of a system during a process is a measure of the maximum useful work done during the change. Therefore, free energy, G of a system is a measure of its capacity of doing useful work. The greater the free energy change, the greater is the amount of work that can be obtained from the process. The relation is useful for assessing the electrical work that may be produced by electrochemical cells and fuel cells.

Free Energy Change and Electrical Work done in a Cell

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In the case of electrochemical cells, free energy change, DG is related to the electrical work done in the cell. If E is the e.m.f of the cell and n mole of electrons are involved, the electrical work done will be DG = -nFEcell, where F is Faraday constant =96500 C. If reactants and products are in theirstandard states, then DGo = -n F Eo, where Eo is the standard cell potential.

Heat Capacity Gibbs Free Energy

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=T+DT = 290 + 0.8 = 290.8 K