Thermal properties of materials

13. Thermal Properties of Materials Content 13.1 Specific heat capacity 13.2 Specific latent heat 13.3 Internal energy 13.4 First law of thermodynamics Learning Outcomes (a) explain using a simple kinetic model for matter why (i) melting and boiling take place without a change in temperature, (ii) the specific latent heat of vaporisation is higher than specific latent heat of fusion for the same substance, (iii) a cooling effect accompanies evaporation.

 (b) define and use the concept of specific heat capacity, and identify the main principles of its determination by electrical methods. (c) define and use the concept of specific latent heat, and identify the main principles of its determination by electrical methods. (d) relate a rise in temperature of a body to an increase in its internal energy. (e) show an understanding that internal energy is determined by the state of the system and that it can be expressed as the sum of a random distribution of kinetic and potential energies associated with the molecules of a system. (f) recall and use the first law of thermodynamics expressed in terms of the change in internal energy, the heating of the system and the work done on the system.
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Thermal properties of materials

Heat is a form of energy associated with temperature. A rise in the temperature of a body means the body is gaining heat energy. It is conveyed in a process of transfer by conduction, convection or radiation from one body to another due to a temperature difference between the two bodies. The rise in temperature of a body is a result of an increase in the energy of the body.

In an ideal gas, temperature is the measure of the average kinetic energy of the molecules, hence it does not depend on how many molecules are present in the gas

Internal Energy of gases, U

The molecules of an ideal gas possess kinetic energy and it is proportional to the thermodynamic temperature of the gas The sum of the kinetic energies of all the molecules due to their random nature is called the internal energy of the ideal gas Not all molecules have the same kinetic energy, because they are moving with different speeds, but the sum of all the kinetic energies will be constant if the gas is kept at a constant temperature For an ideal gas, P.E. is zero and hence U = K.E. The situation for a real gas is different as the molecules exert forces on each other and at any instant there will be a certain potential energy associated with the position the molecules occupy in space For a real gas the molecules also collide with each other and hence p.e and k.e are changing all the time Hence internal energy is the sum of the potential energies and the kinetic energies of the molecules That is, U = P.E. + K.E.
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Internal Energy of matter, U

The idea of internal energy can be extended to all states of matter In a liquid the intermolecular forces are stronger as the molecules are closer together, hence the potential energy contribution is more significant In a solid the potential energy contributions is caused by the strong binding forces between atoms and the kinetic energy contribution is due to the motion of the vibrating atoms The internal energy of a body at a particular temperature is the inherent energy content associated with the bodys molecular structure and is the sum of the kinetic energy (or vibrational/translational energy) and the potential energy of the bodys molecules. The internal energy of a matter in any physical state is actually the sum of the potential (P.E.) and kinetic (K.E.) energies of the atoms or molecules. The potential energy measures the relative positions of the atoms or molecules in the chemical structure of the matter concerned. The kinetic energy measures the vibrational or translational motion of the atoms or molecules. That is, U = P.E. + K.E.
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Why the concept of internal energy

Useful as it helps to distinguish between temperature and heat Temperature is a measure of the average kinetic energy of the molecules and does not depend on the number of molecules present Internal energy is the total energy of the molecules and hence depends on the number of molecules Heat refers to the transfer of energy from one substance to another eg if 10 g of a liquid at 30 C is placed in contact with 100 g of the same liquid at 20 C, the direction of heat flow is from the liquid at 30 C to the liquid at 20 C eventhough the liquid at 20 C has a greater internal energy than the smaller mass of liquid at 30 C
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Specific Heat Capacity, c

The specific heat capacity of a substance is the quantity of heat required to raise the temperature of 1 kg of the substance by 1 degree Therefore if Q is the quantity of heat supplied to the substance of mass m and the temperature rise of it is , then: Q = mc , unit is Joules The quantity mc is termed the heat capacity C of the substance which is the quantity of heat required to raise its temperature by 1 K. i.e. C = mc

Examples of c for some substances

(1) Water = 4200 Jkg-1K-1 (2) Copper = 400 Jkg-1K-1

Specific Latent Heat of Vaporisation, lv

The specific latent heat of vaporisation or evaporation of a liquid is the quantity of heat Q required to convert unit mass of it, at its boiling point, into vapor at the same temperature. The quantitys unit is Jkg-1. Q = m x lv The latent heat of vaporisation is the heat absorbed to cause a given liquid to undergo a liquid-to-vapour phase change at its constant boiling temperature.

Specific Latent Heat of Fusion, lf

The specific latent heat of fusion of a solid is the quantity of heat required Q to convert unit mass of it, at its melting point, into liquid at the same temperature. The quantity has a unit of Jkg-1. Q = m x lf The latent heat of fusion is the heat needed by a solid when it undergoes a solid-to-liquid phase change (i.e., melting) at its constant freezing (or melting) point temperature.

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Temperature Changes

Since = Q/(mc), a smaller mass substance will have a greater fall or gain in its temperature for the same amount of heat loss or gain by the substance at the same temperature. The advantage is reflected in the use of the thermometer to obtain the temperature of an object speedily since the heat capacity at the thermometer junction is small. For water, its higher specific heat capacity results in a much slower rise in its temperature during heating.

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Example

An electric kettle with a 2.0 kW heating element has a heat capacity of 400 Jkg-1. 1.0 kg of water at 20 C is placed in the kettle. The kettle is switched on and it is found that 13 minutes later the mass of water in it is 0.5 kg. Ignoring heat losses, calculate a value for the specific latent heat of vaporization of water. (Specific heat capacity of water = 4200 Jkg-1K-1).

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Solution
Total heat supplied = 2000 x 13 x 60 = 1.56 x 106 J Heat used for kettle = C = 400 x (100 20) = 0.032 x 106 J Heat used to raise temperature of 1 kg of water from 20 to 100C = 1 x 4200 x (100 20) = 0.336 x 106 J Heat used to change water at 100 C to steam at 100 C = 1.56 x 106 - (0.032 x106 + 0.336 x 106) = 1.192 x 106 J Mass of water changed to steam = 1.0 0.5 = 0.5 kg lv = 1.192 x 106 /0.5 = 2.38 x 106 Jkg-1

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The law of conservation of energy and thermodynamics

Energy can neither be created nor destroyed Thermodynamics is the study of processes involving the transfer of heat and the doing of work In thermodynamics it is necessary to define the system under consideration Examples of systems: a) An ideal gas in a cylinder fitted with a piston b) An electric heating coil in a container of liquid

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Transfer of energy
We have said that work is done when energy is transferred by mechanical means We have also said that heat is a transfer of energy due to a difference in temperature Work and heat both involve a transfer of energy, but by different means We have also learnt that the internal energy of a system is the total energy, ke and pe of the various parts of the system For a system consisting of an ideal gas, the internal energy is simply the total ke of all the atoms and molecules of the gas If heat were added to this system or work is done on it, it is transformed and appears as an increase to the internal energy of the gas as by the law of conservation of energy the energy cannot just disappear This addition of energy shows up as an increase in temperature
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First Law of Thermodynamics

The first law of thermodynamics states that the total energy in a closed system is always constant which is basically a restatement of the Principle of Conservation of Energy. The increase in the internal energy of a system is equal to the sum of the heat added to the system and the work done on it The increase in internal energy is given the symbol U, heat added is represented by Q and work done on the system by W

The change in internal energy (U =Uf - Ui) of a system is equal to the heat change (Q) to the system plus any associated work done (W) to the system.
That is, U = Q + W Alternatively, U is equal to Q minus the work done W by the system. That is, U = Q - W
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Sign Convention: Q - is positive if heat is added to/absorbed by, the system Q - is negative if given off by the system W - is positive if work is done on the system W - is negative if done by the system U - is positive if an increase of internal energy i.e. overall gained by the system U - is negative if overall lost by the system The internal energy of a system is therefore dependent on the state of the system at the point of time and is independent of the process or path through which the system is brought from its initial to its final state. The state of a system is defined by its pressure p , volume V and absolute temperature T.
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Eg: Work Done by an Expanding Gas

Consider a gas of pressure p contained in a cylinder fitted with a frictionless piston of cross-sectional area A. The force therefore F acting on the piston is pA. The cylinder and piston are insulated so that no heat can enter or leave the gas If work is done on the gas by pushing the piston in, W is positive Hence U = 0 + W If the piston moves through a small distance l such that p remains constant through out the expansion process, the work done by the expanding gas W is given by: W = Fl = pAl = pV When a gas is warmed so that it expands to increase its volume by V, the heat supplied Q goes towards increasing the internal energy of the gas U as well as doing an external work given by: U = Q + p V

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Eg: an electric kettle containing water

The heater element provides heat to the system, i.e Q No mechanical work is done on or by the water i.e W = 0 U = Q + 0 Hence internal energy and temperature rises

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Change of state
When a substance changes from solid to liquid, intermolecular bonds are broken, thus increasing the potential energy component of the internal energy During the melting process the temperature does not change and therefore the kinetic energy of the molecules does not change Most substances expand on melting, thus external work is done i.e thermal energy is supplied to the system and this thermal energy is the latent heat External work done is much greater during vaporisation and thus the latent heat of vaporisation is much greater than latent heat of fusion e.g for water c = 4.20 x 103 Jkg-1 Lf = 3.36 x 105 Jkg-1 Lv = 2.26 x 106 Jkg-1 20

Example
200 J of heat is added to a system, which does 150 J of work. Find the change in internal energy of the system.

Solution U = Q + W = 200 - 150 = 50 J

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Recap

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What about solids ?

If we think of gases and liquids as having large numbers of atoms, ions or molecules in rapid random motion, then the microscopic model explains that: for solids, due to their rigidity, the atoms are held in more less fixed vibration positions by much stronger inter-atomic forces Atoms in solids can still move but are restricted ito vibration about their equilibrium positions In the change of state from a solid to liquid to gas, work must be done to break the rigid inter-atomic forces so that the atoms can move freely i.e. energy must be applied to change the state

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Kinetic theory model

Melting We think of molecules, ions or atoms as having definite equilibrium positions, but vibrating about these positions with kinetic energy When we heat a solid, the kinetic energy will depend on the temperature As we come to the melting point, the energy supplied does not increase the kinetic energy i.e. temperature of the solid, but instead is used to overcome the forces between the atoms This means that the potential energy is increased, which is the latent heat of fusion

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Boiling
Boiling As heating continues, the atoms can now move freely in the liquid phase, but are still close enough to experience interatomic forces When the temperature is increased to the boiling point, if atoms are to escape, these atomic forces must be overcome i.e. the energy input is the latent heat of vaporisation causing molecules to move far apart When boiling, all particles have the energy to escape

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Evaporation
Boiling only occurs at a particular temperature for a given atmospheric pressure The molecules in a liquid do not all move with the same speed A molecule with a high enough energy may escape from the attractive forces of the molecules in the surface of the liquid This process can take place at any temperature However the higher the temperature the greater the loss of molecules Evaporation increases with the rate of increase of temperature of the surroundings Loss of the fastest molecules means the average speed and kinetic energy of those remaining falls, causing a temperature fall i.e. cooling effect Evaporation only takes place on the surface
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Isothermal Change

An isothermal expansion or compression is one where a gas expands or is compressed at a constant temperature. So for a certain mass of a gas, the relations between the pressure and volume is that which obeys Boyles laws where pV = constant. Therefore Q = W where U = 0.

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Example
An ideal gas expands isothermally, doing 250 J of work. What is the change in internal energy ? How much heat is absorbed in the process?

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Adiabatic Change

An adiabatic expansion or compression is one where no heat enters or leaves the gas. In an adiabatic expansion, the external work is done wholly at the expense of the internal energy of the gas, and the gas therefore cools. In an adiabatic compression, all the work done on the gas results in a rise in the gass temperature. Therefore U = -W where Q = 0.

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Refrigerators and the 2nd Law of thermodynamics

The 2nd law of thermodynamics states that it is impossible to produce an engine that will generate work by extracting heat without expelling some waste heat to a lower temperature sink A refrigerator is a heat pump which transfers internal energy from objects placed in the refrigerator to the surroundings. The amount of heat transferred to the surroundings Q1 is equal to the heat from the interior Q2 plus heat converted from the electrical mains W.

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