Thermal Properties of Matter
Temperature and Thermal Expansion · Calorimetry and Change of State · Heat Transfer
Temperature and Thermal Expansion
We all have a common-sense idea of hot and cold. When a body gets heat, its size or its physical state may change. These changes follow definite laws. All the properties of matter that change because of heat are called its thermal properties. This chapter covers heat, how heat is measured and how heat moves from one place to another.
1.1Temperature and Heat
Temperature is the degree of hotness or coldness of a body. It tells how hot or cold the body is. Temperature is always a relative measure.
Take two bodies at temperatures and , with .
It is the hotter body of the two.
It is the colder body of the two.
When a body is heated, it may expand. Its physical state may also change.
Heat is the form of energy that flows from a hotter body to a colder body because of the temperature difference between them.
Heat transfer is a non-mechanical process. No mechanical work is done when heat flows.
One calorie is the heat required to warm 1 g of water by 1 °C, from 14.5 °C to 15.5 °C.
1.2Caloric and Dynamic Theory of Heat
This old theory treats heat as a fluid called caloric. Caloric was thought to be invisible, weightless and odourless.
Every substance is made of molecules. This is true for solids, liquids and gases. The molecules are always in continuous random motion.
A molecule can have three types of motion. Which types it has depends on the nature and the temperature of the substance.
The molecule moves along a straight line. It is common in gases.
The molecule moves to and fro about its mean position. It is the main motion in solids. It also occurs in liquids and gases.
The molecule spins about its own axis. This motion usually occurs at high temperature.
Each type of motion gives kinetic energy to the molecules. The heat of a body is its total thermal energy. It is the sum of the kinetic energies of all its molecules, due to their translational, vibrational and rotational motion.
1.3Measurement of Temperature
Temperature is a fundamental physical quantity, so we need to measure it. It is measured on fixed scales.
A thermometer is an instrument that measures temperature. It is calibrated, so that each temperature gets a number.
Temperature is measured in these units:
Many physical properties of materials change enough with temperature. Such a property can be used to make a thermometer. The common ones are:
- change in the volume of a liquid with temperature
- change in the pressure or volume of a gas with temperature
- change in the resistance of a metal with temperature
- change in the thermo-emf of a thermocouple junction with temperature, etc.
Every standard scale needs two reference points. For water, these are the ice point and the steam point. At these points pure water freezes and boils, under standard pressure.
Ice point 32 °F, steam point 212 °F. The gap is split into 180 equal parts.
Ice point 0 °C, steam point 100 °C. The gap is split into 100 equal parts.
Plot the Fahrenheit temperature against the Celsius temperature . The graph is a straight line.
A change of 100 °C on the Celsius scale is the same as a change of 180 °F on the Fahrenheit scale. So when .
One kelvin and one Celsius degree have the same size. So the two scales differ only by a fixed number:
| S.No. | Scale | Unit | Ice point (lower fixed point) | Steam point (upper fixed point) |
|---|---|---|---|---|
| 1. | Celsius scale | degree Celsius (°C) | 0 °C | 100 °C |
| 2. | Fahrenheit scale | degree Fahrenheit (°F) | 32 °F | 212 °F |
| 3. | Réaumur scale | degree Réaumur (°R) | 0 °R | 80 °R |
| 4. | Kelvin scale | kelvin (K) | 273.15 K | 373.15 K |
where, , , and are the readings of the same temperature on the Celsius, Fahrenheit, Réaumur and Kelvin scales.
1.4Constant-Volume Gas and Platinum Resistance Thermometers
The volume of the gas is kept constant. Its pressure is noted at four temperatures:
Here the resistance of a platinum wire is noted at four temperatures:
1.5Ideal Gas Equation
Different liquids expand differently. So two such thermometers give different readings, except at the fixed points.
It gives the same reading, no matter which gas is used.
At low density, all gases expand in the same way. Three quantities describe the behaviour of a gas:
At constant temperature, the pressure of a given mass of gas is inversely proportional to its volume. So , that is, = constant.
Given by the English chemist Robert Boyle (1627–1691).
At constant pressure, the volume of a given mass of gas is directly proportional to its temperature. So , that is, = constant.
Given by the French scientist Jacques Charles (1747–1823).
This relation is called the ideal gas law. For a given amount of gas, its general form is:
where, = number of moles of the gas, = universal gas constant
The ideal gas equation gives . If the volume is kept constant, then . That is why a gas can measure temperature in a constant-volume gas thermometer.
1.6Absolute Zero Temperature
There is no upper limit to temperature. But there is a sharp lower limit. No body can be colder than this lowest temperature. It is called absolute zero temperature.
- Keep a low-density gas at constant volume. Plot its pressure against its temperature in °C.
- Extend the straight line backwards (extrapolate it). It meets the temperature axis at −273.15 °C.
- The British scientist Lord Kelvin named this temperature absolute zero. It is written as 0 A or 0 K.
- At this temperature, the pressure and volume of the gas would become zero.
Absolute zero is the lowest temperature, −273.15 °C. At this temperature a gas would have zero volume (or zero pressure), and all molecular motion stops.
Imagine a temperature below absolute zero. The volume of the gas would then be negative, which is impossible. So absolute zero is the lowest temperature that can exist.
Repeat the experiment with different low-density gases , and . Each gas gives a straight line with its own slope.
When extended, all the lines meet the temperature axis at the same point, −273.15 °C. So every gas gives the same absolute zero.
A temperature measured on the Kelvin scale is called the absolute temperature.
The Kelvin scale itself is called the absolute scale.
1.7Thermal Expansion
The metal lid of a glass bottle is sometimes screwed on very tightly. To open it, we dip the lid in hot water for a while. The metal lid expands and becomes loose. Now it unscrews easily.
So, when a material gets heat, its temperature rises. Then its length, area and volume can change.
Thermal expansion is the change in the size (dimensions) of a body when it is heated.
Thermal expansion is of three types:
Increase in length.
Increase in area.
Increase in volume.
1.8Linear Expansion
Linear expansion is the increase in the length of a body when its temperature rises.
A rod has length at temperature . On heating to , its length becomes . The fractional change in length is:
The increase in length is proportional to the original length. It is also proportional to the rise in temperature.
where, = coefficient of linear expansion, = original length, = rise in temperature
The coefficient of linear expansion of a solid is the change in length of a rod of unit length when its temperature rises by one degree. It is measured in °C⁻¹ or K⁻¹.
1.9Area Expansion
Area expansion is the increase in the area of a surface when its temperature rises.
A plate has area at temperature . On heating to , its area becomes . The fractional change in area is:
where, = coefficient of area expansion. It depends on the nature of the material of the plate.
The coefficient of area expansion of a metal sheet is the change in area of a sheet of unit area when its temperature rises by one degree. It is measured in °C⁻¹ or K⁻¹.
1.10Volume Expansion
Volume expansion is the increase in the volume of a body when its temperature rises.
A body has volume at temperature . On heating to , its volume becomes . The fractional change in volume is:
where, = coefficient of volume expansion, so that
The coefficient of volume (cubical) expansion of a substance is the change in volume of a body of unit volume when its temperature rises by one degree. It is measured in °C⁻¹ or K⁻¹.
- is a property of the material. But it is not strictly a constant.
- In general, depends on temperature. The graph shows this for copper.
- Its value first increases with temperature.
- It becomes constant at high temperature, above about 500 K.
All coefficients of expansion have the dimension . Their SI unit is per kelvin .
1.11Relation Among the Coefficients of Expansion
Write the original size simply as , or (that is, , and ). Then the three coefficients are:
So, and
For a given solid, , and are constant only at a given temperature.
1.12Anomalous Expansion of Water
- Water behaves in an unusual (anomalous) way. Between 0 °C and 4 °C, it contracts on heating.
- Cool some water below room temperature. Its volume decreases until it reaches 4 °C.
- Below 4 °C, its volume increases. So its density decreases.
- The second graph shows the density of water from 0 °C to 10 °C. The density is maximum at 4 °C. It falls on both sides of 4 °C.
In winter, a lake cools towards 4 °C. The surface water gives heat to the air. It becomes denser and sinks. The warmer, lighter water from the bottom rises up.
When the top water cools below 4 °C, it becomes less dense. So it stays at the surface and freezes there. The water below stays liquid. This lets water animals stay alive and move freely near the bottom.
1.13Expansion of Solids, Liquids and Gases
At ordinary temperature, they expand very little compared with gases.
For a liquid, is nearly independent of temperature.
Keep the pressure constant. Start from the ideal gas equation:
1.14Thermal Strain and Thermal Stress
Fix both ends of a metal rod rigidly, so that it cannot expand or contract. Now change its temperature. Thermal strain and thermal stress develop in the rod.
Why? When the temperature rises, the rod tries to expand. But both its ends are fixed. So the rod pushes on the supports with a force.
Let a rod of length be heated through . If it were free, its length would increase by:
The ends are fixed, so the rod cannot expand. A compressive thermal strain develops in it:
This strain produces a thermal stress:
where, = coefficient of linear expansion of the rod's material
where, = Young's modulus of the rod's material
Calorimetry and Change of State
2.1Heat Capacity and Specific Heats
The heat needed to change the temperature of a substance depends on three things:
A substance absorbs or gives out heat when its temperature changes. A quantity called heat capacity describes this.
The heat capacity of a body is the amount of heat needed to change its temperature by one unit (1 °C or 1 K). Its SI unit is J K⁻¹.
where, = heat absorbed or given out by the body, = change in its temperature
The water equivalent of a body is the mass of water that has the same heat capacity as the body. Its unit is the gram.
The specific heat capacity (or specific heat) of a substance is the heat required to increase the temperature of unit mass (1 kg) of it by one unit (1 K). Its SI unit is J kg⁻¹ K⁻¹.
where, = mass of the substance, = its heat capacity, = heat given, = rise in temperature
Water has the highest specific heat capacity among common substances, . So water is used:
- as a coolant in car radiators, and
- as a heater in hot-water bags.
The molar specific heat capacity of a substance (gas) is the heat required to increase the temperature of 1 mole of it by one unit (1 K). Its SI unit is J mol⁻¹ K⁻¹.
where, = number of moles of the substance (gas)
Number of moles . Here is the mass of the substance and is its molecular mass. So .
Put in the formula for :
But , the specific heat capacity. So:
So equals the molecular mass multiplied by the specific heat .
The heat needed to raise the temperature of 1 mole of a gas by one unit, at constant pressure.
The heat needed to raise the temperature of 1 mole of a gas by 1 °C, at constant volume.
Both kinds of heat capacity are very useful in calorimetry.
2.2Calorimetry and Calorimeter
Calorimetry is the branch of physics in which we measure heat.
Put a hot body in contact with a cold body. Heat flows from the hot body to the cold body. It keeps flowing until both bodies reach the same temperature.
The total heat given out by the hotter body is equal to the total heat taken in by the colder body.
Let body 1 (hotter) have mass and specific heat . Let body 2 (colder) have mass and specific heat . Then:
where, = fall in temperature of the hot body, = rise in temperature of the cold body
A system is isolated when no heat is exchanged between the system and its surroundings. In calorimetry, we assume that no heat escapes to the surroundings.
A calorimeter is a device used to measure quantities of heat.
- It has a cylindrical copper vessel with a stirrer.
- The vessel sits inside a wooden jacket. The gap between them is packed with a heat-insulating material such as glass wool. So the calorimeter is thermally isolated from the surroundings.
- The lid has holes. A thermometer and the stirrer go into the vessel through them.
Heat lost by radiation is cut down further by polishing two surfaces:
- the outer surface of the calorimeter, and
- the inner surface of the jacket.
Bodies at different temperatures are mixed in the calorimeter. Heat is exchanged among the bodies and also with the calorimeter. If no heat is lost to the surroundings, the principle of calorimetry gives:
2.3Change of State
Change of state is the process in which a substance changes from one state to another.
Matter usually exists in three states:
e.g. ice
e.g. water
e.g. steam
A substance can change from one state to another by taking in heat or giving out heat. The common changes of state are:
These changes happen when heat is exchanged between the substance and its surroundings.
Besides solid, liquid and gas, there is a fourth state of matter. It is called plasma.
Heat a substance to a very high temperature. Many electrons of its atoms become free from the nucleus. The free electrons and the positive ions together form plasma.
- Put a few ice cubes at 0 °C in a beaker. Heat them slowly on a source that gives heat at a constant rate.
- Stir the mixture of ice and water all the time. Note the temperature every minute.
- The temperature–time graph looks like the one shown.
- Heat is supplied all the time. Yet the temperature does not change as long as there is ice in the beaker.
- The temperature stays constant until all the ice has melted.
- So, during melting, the solid and liquid states exist together in thermal equilibrium.
- After all the ice has melted, keep heating. The temperature now starts to rise. It rises until it reaches about 100 °C. Then it becomes steady again. This happens at time on the graph.
- The heat now changes the water from liquid to vapour. The temperature stays constant until all the water has turned into vapour.
With a constant supply of heat, a change of state takes place with no change in temperature.
2.4Terms Related to Change of State
The change from solid to liquid is called melting. The temperature at which a solid starts to turn into liquid is its melting point.
The change from liquid to solid is called fusion (freezing). The temperature at which a liquid starts to freeze is its freezing point.
The change from liquid to vapour (gas) is called vaporisation. During this change, the temperature stays constant. The liquid and vapour exist together in thermal equilibrium. This temperature is the boiling point of the liquid.
The change from solid directly to vapour is called sublimation. The substance does not pass through the liquid state. e.g. camphor, naphthalene balls.
The normal melting point of a substance is its melting point at standard atmospheric pressure.
Boiling point = 100 °C
Boiling point = 128 °C
2.5Triple Point
The temperature of a substance stays constant during a change of state (phase change).
A graph between the temperature and the pressure of a substance is called its phase diagram, or p–T diagram.
The phase diagrams of water and CO₂ divide the p–T plane into three regions: the solid region, the liquid region and the vapour region.
Three curves separate these regions: the sublimation curve, the fusion curve and the vaporisation curve. On these curves, two phases exist together: solid and vapour, solid and liquid, and liquid and vapour.
The triple point of a substance is the temperature and pressure at which all three phases (solid, liquid and vapour) exist together.
2.6Latent Heat
The latent heat of a substance is the amount of heat per unit mass transferred during a change of state, with no change in temperature.
Latent heat is written as . Its SI unit is J kg⁻¹. Latent heat depends on pressure. So its value is usually given at standard atmospheric pressure.
Let a mass of a substance change from one state to another. The heat needed is:
where, = heat of transformation, = mass of the substance, = latent heat. So the heat needed depends on the mass and on the latent heat.
The latent heat for the change between solid and liquid. It is also called the heat of fusion.
The latent heat for the change between liquid and gas. It is also called the heat of vaporisation.
For water, and . This means:
- 3.33 × 10⁵ J of heat melts 1 kg of ice at 0 °C.
- 22.6 × 10⁵ J of heat changes 1 kg of water at 100 °C into steam.
- The graph shows that the temperature stays constant while heat is added (or removed) during a change of state.
- The sloping lines for ice, water and steam have different slopes. So the specific heats of the different states are not equal.
2.7Mechanical Equivalent of Heat
We can also raise the temperature of a body by doing mechanical work on it.
The mechanical equivalent of heat is the number of joules of mechanical work needed to raise the temperature of 1 g of water by 1 °C.
Its unit is J/cal. It is only a number that converts heat in calories into work in joules.
where, = work done, in joules (SI unit), = mechanical equivalent of heat (J/cal), = heat given or taken out, in calories (CGS unit)
Heat Transfer
3.1Modes of Heat Transfer
Heat flows from one body to another because of a temperature difference. It can flow as radiation, through molecular vibrations or through molecular displacement. All these processes of heat flow together are called heat transfer.
There are three modes of heat transfer:
3.2Conduction and Thermal Conductivity
Conduction is the transfer of heat through molecular vibrations (molecular collisions). The average position of the molecules does not change. So there is no movement of matter as a whole. In solids, heat is usually transferred by conduction.
Thermal conductivity is the ability of a material to conduct heat through it. We measure it by the heat that flows per second through the material when a fixed temperature difference is kept across it.
- Length of the rod . Area of cross-section .
- Temperatures of its two ends and .
- The rod is in the steady state.
In the steady state, the heat that flows through any section of the rod is:
So the rate of heat flow does not depend on time. It is:
Since , the total heat that flows in time is:
where, = coefficient of thermal conductivity of the material. A larger means the material conducts heat faster.
The thermal conductivity of a material changes slightly with temperature. But over the normal range of temperature, we can take it as constant.
Put , , and . Then .
So the coefficient of thermal conductivity of a material is the heat that flows in unit time through a unit cube of it, when its opposite faces differ in temperature by one degree.
Steady stateThe temperature of each part of the body stays constant while heat flows through it
Metals conduct heat much better than non-metals. Metals have a large number of free electrons. These electrons carry heat from the hotter part to the colder part.
3.3Heat Current and Thermal Resistance
The heat current is the rate of flow of heat. Its SI unit is J/s or watt (W). Its dimensions are .
= potential difference, = electrical resistance
= temperature difference, = thermal resistance
So behaves like a thermal current (heat flow), and behaves like a thermal resistance.
3.4Rods in Series and in Parallel
When two or more rods are joined together, the equivalent thermal conductivity of the whole set-up changes.
For resistances in series, . Use for each rod:
If the rods have equal lengths, , then . This gives:
where, = equivalent thermal conductivity of the two rods joined end to end
For resistances in parallel, . Take rods of equal length and equal area. Together they have area :
for two rods of equal length and equal area, placed side by side
3.5Convection
Convection is the transfer of heat by the actual movement of matter from a region of higher temperature to a region of lower temperature. It takes place only in fluids, that is, in liquids and gases.
Convection is of two types:
The heated material is forced to move, for example by a blower or a pump. It carries heat with it.
e.g. Heat transfer in the human body.
The heated material moves because of a difference in density.
e.g. Heat transfer in water being heated.
- In the day, the land heats up faster than the sea. Water has a greater specific heat. Mixing currents also spread the heat through its large volume.
- The hot air above the land expands, becomes less dense and rises. Cooler air from the sea takes its place. The warm air from the land moves towards the sea and completes the cycle.
- So a breeze blows from the sea to the land. It is called a sea breeze.
- At night, the opposite happens. The land cools faster than the sea.
- The warm air above the sea rises. Cooler air from the land takes its place.
- So a breeze blows from the land to the sea. It is called a land breeze.
- The equator and the poles of the Earth get unequal heat from the Sun. Air near the surface at the equator is hot. Air in the upper atmosphere at the poles is cool.
- So a convection current forms between them. Air at the equator rises and moves out towards the poles. It then comes down and flows back towards the equator.
- The rotation of the Earth changes this convection current. Air near the equator has an eastward speed of 1600 km/h. Close to the poles, this speed is zero.
- So the air comes down not at the poles but at about 30° N latitude. It then returns to the equator. This is called the trade wind.
The trade wind is the steady wind that blows near the Earth's surface from the north-east towards the equator. It is an example of natural convection.
3.6Radiation
Radiation is the transfer of heat from one point to another without warming the medium in between. The heat travels as thermal radiation, also called radiant energy or simply radiation.
The word radiation has two meanings:
A body gives out energy. The energy travels through space and falls on another body.
The energy itself that travels through space.
Heat from the Sun reaches the Earth by radiation. It crosses millions of kilometres of empty space, with no material medium in between.
Thermal radiation is the electromagnetic radiation given out by a body because of its temperature.
e.g. Radiation from a red-hot iron. Light from a filament lamp.
Thermal radiation falling on a body is partly reflected and partly absorbed.
- The heat a body absorbs by radiation depends on its colour.
- A body has a particular colour because it reflects back radiation of that wavelength.
A black body is a body that absorbs all the radiation falling on it. The radiation given out by a black body is called black body radiation.
3.7Absorptive Power and Emissivity
The absorptance , or absorptive power, of a body is the ratio of the thermal radiation it absorbs in a given time to the total thermal radiation falling on it in the same time.
The emissive power of a body is the radiant energy it gives out per unit time per unit surface area, within a unit wavelength range around a wavelength . It is taken at a fixed temperature.
The emissivity of a body is the ratio of its emissive power to the emissive power of a perfect black body at the same temperature.
where, = emissive power of the body, = emissive power of a perfect black body at the same temperature
3.8Stefan–Boltzmann Law
The total energy emitted per second per unit area of a perfect black body is directly proportional to the fourth power of its absolute temperature.
where, = total energy emitted per second per unit area, = absolute temperature, = Stefan–Boltzmann constant (a universal constant)
Suppose the body is not a perfect black body. Let its emissivity be . Then the law becomes:
3.9Wien's Displacement Law
The wavelength at which a black body emits the maximum energy is inversely proportional to its absolute temperature .
where, = Wien's constant
3.10Newton's Law of Cooling
The rate at which a body loses heat is directly proportional to the difference between its temperature and the temperature of its surroundings. This is true only when the difference is small.
where, = rate of loss of heat, = temperature of the body, = temperature of the surroundings, = a constant