Thermocouple

Thermocouple plugged to a multimeter displaying room temperature in °C.

A thermocouple is a device consisting of two different conductors (usually metal alloys) that
produce a voltage proportional to a temperature difference between either end of the pair of
conductors. Thermocouples are a widely used type of temperature sensor for measurement and
control[1] and can also be used to convert a heat gradient into electricity. They are inexpensive, [2]
interchangeable, are supplied with standard connectors, and can measure a wide range of
temperatures. In contrast to most other methods of temperature measurement, thermocouples are
self powered and require no external form of excitation. The main limitation with thermocouples
is accuracy and system errors of less than one degree Celsius (C) can be difficult to achieve.[3]

Any junction of dissimilar metals will produce an electric potential related to temperature.
Thermocouples for practical measurement of temperature are junctions of specific alloys which
have a predictable and repeatable relationship between temperature and voltage. Different alloys
are used for different temperature ranges. Properties such as resistance to corrosion may also be
important when choosing a type of thermocouple. Where the measurement point is far from the
measuring instrument, the intermediate connection can be made by extension wires which are
less costly than the materials used to make the sensor. Thermocouples are usually standardized
against a reference temperature of 0 degrees Celsius; practical instruments use electronic
methods of cold-junction compensation to adjust for varying temperature at the instrument
terminals. Electronic instruments can also compensate for the varying characteristics of the
thermocouple, and so improve the precision and accuracy of measurements.

Thermocouples are widely used in science and industry; applications include temperature
measurement for kilns, gas turbine exhaust, diesel engines, and other industrial processes.
A thermocouple measuring circuit with a heat source, cold junction and a measuring instrument.

Principle of operation
Main article: Seebeck effect

In 1821, the German–Estonian physicist Thomas Johann Seebeck discovered that when any
conductor is subjected to a thermal gradient, it will generate a voltage. This is now known as the
thermoelectric effect or Seebeck effect. Any attempt to measure this voltage necessarily involves
connecting another conductor to the "hot" end. This additional conductor will then also
experience the temperature gradient, and develop a voltage of its own which will oppose the
original. Fortunately, the magnitude of the effect depends on the metal in use. Using a dissimilar
metal to complete the circuit creates a circuit in which the two legs generate different voltages,
leaving a small difference in voltage available for measurement. That difference increases with
temperature, and is between 1 and 70 microvolts per degree Celsius (µV/°C) for standard metal
combinations.

The voltage is not generated at the junction of the two metals of the thermocouple but rather
along that portion of the length of the two dissimilar metals that is subjected to a temperature
gradient. Because both lengths of dissimilar metals experience the same temperature gradient,
the end result is a measurement of the temperature at the thermocouple junction.
Practical use Polynomial Coefficients 0-500 °C[4]
n an (for Type K)
Voltage–temperature relationship 1 25.08355
2 7.860106x10−2
For typical metals used in thermocouples, the output −1
voltage increases almost linearly with the temperature 3 -2.503131x10
difference (ΔT) over a bounded range of temperatures. For 4 8.315270x10−2
precise measurements or measurements outside of the 5 -1.228034x10−2
linear temperature range, non-linearity must be corrected. 6 9.804036x10−4
The nonlinear relationship between the temperature −5
difference (ΔT) and the output voltage (mV) of a 7 -4.413030x10
thermocouple can be approximated by a polynomial: 8 1.057734x10−6
9 -1.052755x10−8

The coefficients an are given for n from 0 to between 5 and 13 depending upon the metals. In
some cases better accuracy is obtained with additional non-polynomial terms. [4] A database of
voltage as a function of temperature, and coefficients for computation of temperature from
voltage and vice-versa for many types of thermocouple is available online.[4]

In modern equipment the equation is usually implemented in a digital controller or stored in a

look-up table;[5] older devices use analog circuits.

Cold junction compensation

Thermocouples measure the temperature difference between two points, not absolute
temperature. To measure a single temperature one of the junctions—normally the cold junction
—is maintained at a known reference temperature, and the other junction is at the temperature to
be sensed.

Having a junction of known temperature, while useful for laboratory calibration, is not
convenient for most measurement and control applications. Instead, they incorporate an artificial
cold junction using a thermally sensitive device such as a thermistor or diode to measure the
temperature of the input connections at the instrument, with special care being taken to minimize
any temperature gradient between terminals. Hence, the voltage from a known cold junction can
be simulated, and the appropriate correction applied. This is known as cold junction
compensation. Some integrated circuits such as the LT1025 are designed to output a
compensated voltage based on thermocouple type and cold junction temperature.

Power production
A thermocouple can produce current, which means it can be used to drive some processes
directly, without the need for extra circuitry and power sources. For example, the power from a
thermocouple can activate a valve when a temperature difference arises. The electrical energy
generated by a thermocouple is converted from the heat which must be supplied to the hot side to
maintain the electric potential. A continuous flow of heat is necessary because the current
flowing through the thermocouple tends to cause the hot side to cool down and the cold side to
heat up (the Peltier effect).

Thermocouples can be connected in series to form a thermopile, where all the hot junctions are
exposed to a higher temperature and all the cold junctions to a lower temperature. The output is
the sum of the voltages across the individual junctions, giving larger voltage and power output.
In a radioisotope thermoelectric generator, the radioactive decay of transuranic elements as a
heat source has been used to power spacecraft on missions too far from the Sun to use solar
power.

Grades
Thermocouple wire is available in several different metallurgical formulations per type,
typically, in decreasing levels of accuracy and cost: special limits of error, standard, and
extension grades.

Extension wire

Extension grade wires made of the same metals as a higher-grade thermocouple are used to
connect it to a measuring instrument some distance away without introducing additional
junctions between dissimilar materials which would generate unwanted voltages; the connections
to the extension wires, being of like metals, do not generate a voltage. In the case of platinum
thermocouples, extension wire is a copper alloy, since it would be prohibitively expensive to use
platinum for extension wires. The extension wire is specified to have a very similar thermal
coefficient of EMF to the thermocouple, but only over a narrow range of temperatures; this
reduces the cost significantly.

The temperature-measuring instrument must have high input impedance to prevent any
significant current draw from the thermocouple, to prevent a resistive voltage drop across the
wire. Changes in metallurgy along the length of the thermocouple (such as termination strips or
changes in thermocouple type wire) will introduce another thermocouple junction which affects
measurement accuracy.

Types
Certain combinations of alloys have become popular as industry standards. Selection of the
combination is driven by cost, availability, convenience, melting point, chemical properties,
stability, and output. Different types are best suited for different applications. They are usually
selected based on the temperature range and sensitivity needed. Thermocouples with low
sensitivities (B, R, and S types) have correspondingly lower resolutions. Other selection criteria
include the inertness of the thermocouple material, and whether it is magnetic or not. Standard
thermocouple types are listed below with the positive electrode first, followed by the negative
electrode.

Type K (chromel{90 percent nickel and 10 percent chromium}–alumel)(Alumel consisting of

95% nickel, 2% manganese, 2% aluminium and 1% silicon) is the most common general purpose
thermocouple with a sensitivity of approximately 41 µV/°C, chromel positive relative to alumel.
[7]
It is inexpensive, and a wide variety of probes are available in its −200 °C to +1350 °C /
-328 °F to +2462 °F range. Type K was specified at a time when metallurgy was less advanced
than it is today, and consequently characteristics may vary considerably between samples. One
of the constituent metals, nickel, is magnetic; a characteristic of thermocouples made with
magnetic material is that they undergo a deviation in output when the material reaches its Curie
point; this occurs for type K thermocouples at around 150 °C.

Type E (chromel–constantan)[5] has a high output (68 µV/°C) which makes it well suited to
cryogenic use. Additionally, it is non-magnetic.

Type J (iron–constantan) has a more restricted range than type K (−40 to +750 °C), but higher
sensitivity of about 55 µV/°C.[2] The Curie point of the iron (770 °C)[8] causes an abrupt change
in the characteristic, which determines the upper temperature limit.

Type N (Nicrosil–Nisil) (Nickel-Chromium-Silicon/Nickel-Silicon) thermocouples are suitable

for use at high temperatures, exceeding 1200 °C, due to their stability and ability to resist high
temperature oxidation. Sensitivity is about 39 µV/°C at 900 °C, slightly lower than type K.
Designed to be an improved type K due to increased stability at higher temperatures, it is
becoming more popular, though the differences may or may not be substantial enough to warrant
a change.

Platinum types B, R, and S

Types B, R, and S thermocouples use platinum or a platinum–rhodium alloy for each conductor.
These are among the most stable thermocouples, but have lower sensitivity than other types,
approximately 10 µV/°C. Type B, R, and S thermocouples are usually used only for high
temperature measurements due to their high cost and low sensitivity.

B
Type B thermocouples use a platinum–rhodium alloy for each conductor. One conductor
contains 30% rhodium while the other conductor contains 6% rhodium. These thermocouples are
suited for use at up to 1800 °C. Type B thermocouples produce the same output at 0 °C and
42 °C, limiting their use below about 50 °C.

Type R thermocouples use a platinum–rhodium alloy containing 13% rhodium for one conductor
and pure platinum for the other conductor. Type R thermocouples are used up to 1600 °C.

Type S thermocouples are constructed using one wire of 90% Platinum and 10% Rhodium (the
positive or "+" wire) and a second wire of 100% platinum (the negative or "-" wire). Like type R,
type S thermocouples are used up to 1600 °C. In particular, type S is used as the standard of
calibration for the melting point of gold (1064.43 °C).

Type T (copper–constantan) thermocouples are suited for measurements in the −200 to 350 °C
range. Often used as a differential measurement since only copper wire touches the probes. Since
both conductors are non-magnetic, there is no Curie point and thus no abrupt change in
characteristics. Type T thermocouples have a sensitivity of about 43 µV/°C.

Type C (tungsten 5% rhenium – tungsten 26% rhenium) thermocouples are suited for
measurements in the 0 °C to 2320 °C range. This thermocouple is well-suited for vacuum
furnaces at extremely high temperatures. It must never be used in the presence of oxygen at
temperatures above 260 °C.

Type M thermocouples use a nickel alloy for each wire. The positive wire (20 Alloy) contains
18% molybdenum while the negative wire (19 Alloy) contains 0.8% cobalt. These
thermocouples are used in vacuum furnaces for the same reasons as with type C. Upper
temperature is limited to 1400 °C. It is less commonly used than other types.

Chromel-gold/iron

In chromel-gold/iron thermocouples, the positive wire is chromel and the negative wire is gold
with a small fraction (0.03–0.15 atom percent) of iron. It can be used for cryogenic applications
(1.2–300 K and even up to 600 K). Both the sensitivity and the temperature range depends on the
iron concentration. The sensitivity is typically around 15 µV/K at low temperatures and the
lowest usable temperature varies between 1.2 and 4.2 K.
Laws for thermocouples
Law of homogeneous material

A thermoelectric current cannot be sustained in a circuit of a single homogeneous material by the

application of heat alone, regardless of how it might vary in cross section. In other words,
temperature changes in the wiring between the input and output do not affect the output voltage,
provided all wires are made of the same materials as the thermocouple. No current flows in the
circuit made of a single metal by the application of heat alone.

Law of intermediate materials

The algebraic sum of the thermoelectric emfs in a circuit composed of any number of dissimilar
materials is zero if all of the junctions are at a uniform temperature. So If a third metal is inserted
in either wire and if the two new junctions are at the same temperature, there will be no net
voltage generated by the new metal.

Law of successive or intermediate temperatures

If two dissimilar homogeneous materials produce thermal emf1 when the junctions are at T1 and
T2 and produce thermal emf2 when the junctions are at T2 and T3, the emf generated when the
junctions are at T1 and T3 will be emf1 + emf2,provided T1<T2<T3.

Aging of thermocouples
Thermoelements are often used at high temperatures and in reactive furnace atmospheres. In this
case the practical lifetime is determined by aging. The thermoelectric coefficients of the wires in
the area of high temperature change with time and the measurement voltage drops. The simple
relationship between the temperature difference of the joints and the measurement voltage is
only correct if each wire is homogeneous. With an aged thermocouple this is not the case.
Relevant for the generation of the measurement voltage are the properties of the metals at a
temperature gradient. If an aged thermocouple is pulled partly out of the furnace, the aged parts
from the region previously at high temperature enter the area of temperature gradient and the
measurement error is significantly increased. However an aged thermocouple that is pushed
deeper into the furnace gives a more accurate reading.[citation needed]

Thermocouple comparison
The table below describes properties of several different thermocouple types. Within the
tolerance columns, T represents the temperature of the hot junction, in degrees Celsius. For
example, a thermocouple with a tolerance of ±0.0025×T would have a tolerance of ±2.5 °C at
1000 °C.

Type Temperature Temperature Tolerance Tolerance IEC BS ANSI

 range °C range °C class one class two Color Color Color
(continuous) (short term) (°C) (°C) code code code
±1.5
between ±2.5
−40 °C between
and 375 −40 °C and
−180 to °C 333 °C
K 0 to +1100
+1300 ±0.004×T ±0.0075×T
between between
375 °C 333 °C and
and 1000 1200 °C
°C
±1.5
between ±2.5
−40 °C between
and 375 −40 °C and
°C 333 °C
J 0 to +750 −180 to +800
±0.004×T ±0.0075×T
between between
375 °C 333 °C and
and 750 750 °C
°C
±1.5
between ±2.5
−40 °C between
and 375 −40 °C and
−270 to °C 333 °C
N 0 to +1100
+1300 ±0.004×T ±0.0075×T
between between
375 °C 333 °C and
and 1000 1200 °C
°C
±1.0
between 0
±1.5
°C and
between 0
1100 °C
°C and 600
±[1 +
°C Not
R 0 to +1600 −50 to +1700 0.003×(T
±0.0025×T defined.
− 1100)]
between
between
600 °C and
1100 °C
1600 °C
and 1600
°C
S 0 to 1600 −50 to +1750 ±1.0 ±1.5 Not
between 0 between 0 defined.
°C and °C and 600
 1100 °C
±[1 +
°C
0.003×(T
±0.0025×T
− 1100)]
between
between
600 °C and
1100 °C
1600 °C
and 1600
°C
No No
±0.0025×T
standard standard
+200 to Not between Not
B 0 to +1820 use use
+1700 Available 600 °C and defined.
copper copper
1700 °C
wire wire
±0.5
between ±1.0
−40 °C between
and 125 −40 °C and
°C 133 °C
T −185 to +300 −250 to +400
±0.004×T ±0.0075×T
between between
125 °C 133 °C and
and 350 350 °C
°C
±1.5
between ±2.5
−40 °C between
and 375 −40 °C and
°C 333 °C
E 0 to +800 −40 to +900
±0.004×T ±0.0075×T
between between
375 °C 333 °C and
and 800 900 °C
°C
Reproducibility 0.2%
of the voltage; each
Chromel/AuFe −272 to +300 n/a
sensor needs
individual calibration.

Applications
Thermocouples are suitable for measuring over a large temperature range, up to 2300 °C. They
are less suitable for applications where smaller temperature differences need to be measured with
high accuracy, for example the range 0–100 °C with 0.1 °C accuracy. For such applications
thermistors, silicon bandgap temperature sensors and resistance temperature detectors are more
suitable. Applications include temperature measurement for kilns, gas turbine exhaust, diesel
engines, and other industrial processes.

Steel industry

Type B, S, R and K thermocouples are used extensively in the steel and iron industries to
monitor temperatures and chemistry throughout the steel making process. Disposable,
immersible, type S thermocouples are regularly used in the electric arc furnace process to
accurately measure the temperature of steel before tapping. The cooling curve of a small steel
sample can be analyzed and used to estimate the carbon content of molten steel.

Heating appliance safety

Many gas-fed heating appliances such as ovens and water heaters make use of a pilot flame to
ignite the main gas burner when required. If it goes out gas may be released, which is a fire risk
and a health hazard. To prevent this some appliances use a thermocouple in a fail-safe circuit to
sense when the pilot light is burning. The tip of the thermocouple is placed in the pilot flame,
generating a voltage which operates the supply valve which feeds gas to the pilot. So long as the
pilot flame remains lit, the thermocouple remains hot, and the pilot gas valve is held open. If the
pilot light goes out, the thermocouple temperature falls, causing the voltage across the
thermocouple to drop and the valve to close. Some combined main burner and pilot gas valves
(mainly by honeywell) reduce the power demand to within the range of a single universal
thermocouple heated by a pilot (25mV open circuit falling by half with the coil connected to
10~12mV @ 0.2~0.25A typically) by sizing the coil to be able to hold the valve open against a
light spring, only after the initial turning on force is provided by a the user pressing and holding
a knob to compress the spring during first lighting. These systems are identifiable by the 'press
and hold for x minutes' in the pilot lighting instructions. (The holding current requirement of
such a valve is much less than a bigger solenoid designed for pulling the valve in from closed
would require.) Special test sets are made to confirm the valve let-go and holding currents as an
ordinary milliameter cannot be used as it introduces more resistance than the gas valve coil.
Apart from testing the open circuit voltage of the thermocouple, and the near short-circuit DC
continuity through the thermocouple gas valve coil, the easiest non-specialist test is substitution
of a known good gas valve.

Some systems, known as millivolt control systems, extend the thermocouple concept to both
open and close the main gas valve as well. Not only does the voltage created by the pilot
thermocouple activate the pilot gas valve, it is also routed through a thermostat to power the
main gas valve as well. Here, a larger voltage is needed than in a pilot flame safety system
described above, and a thermopile is used rather than a single thermocouple. Such a system
requires no external source of electricity for its operation and so can operate during a power
failure, provided all the related system components allow for this. Note that this excludes
common forced air furnaces because external power is required to operate the blower motor, but
this feature is especially useful for un-powered convection heaters. A similar gas shut-off safety
mechanism using a thermocouple is sometimes employed to ensure that the main burner ignites
within a certain time period, shutting off the main burner gas supply valve should that not
happen.

Out of concern for energy wasted by the standing pilot, designers of many newer appliances have
switched to an electronically controlled pilot-less ignition, also called intermittent ignition. With
no standing pilot flame, there is no risk of gas buildup should the flame go out, so these
appliances do not need thermocouple-based pilot safety switches. As these designs lose the
benefit of operation without a continuous source of electricity, standing pilots are still used in
some appliances. The exception is later model instantaneous water heaters that use the flow of
water to generate the current required to ignite the gas burner, in conjunction with a
thermocouple as a safety cut-off device in the event the gas fails to ignite, or the flame is
extinguished.

Thermopile radiation sensors

See also: bolometer

Thermopiles are used for measuring the intensity of incident radiation, typically visible or
infrared light, which heats the hot junctions, while the cold junctions are on a heat sink. It is
possible to measure radiative intensities of only a few μW/cm2 with commercially available
thermopile sensors. For example, some laser power meters are based on such sensors.

Manufacturing

Thermocouples can generally be used in the testing of prototype electrical and mechanical
apparatus. For example, switchgear under test for its current carrying capacity may have
thermocouples installed and monitored during a heat run test, to confirm that the temperature rise
at rated current does not exceed designed limits.

Radioisotope thermoelectric generators

Thermopiles can also be applied to generate electricity in radioisotope thermoelectric generators.

Thermocouple Circuit

A typical thermocouple circuit can be illustrated as follows:

Typical Thermocouple Circuit

Suppose that the Seebeck coefficients of two dissimilar metallic materials, metal A and metal B,
and the lead wires are SA, SB, and SLead respectively. All three Seebeck coefficients are functions
of temperature. The voltage output Vout measured at the gage (see schematic above) is,

where TRef is the temperature at the reference point, TTip is the temperature at the probe tip. Note
that mathematically the voltage induced by the temperature and/or material mismatch of the lead
wires cancels, whereas in reality the lead wires will introduce noise into the circuit.

If the Seebeck coefficient functions of the two thermocouple wire materials are pre-calibrated
and the reference temperature TRef is known (usually set by a 0°C ice bath), the temperature at the
probe tip becomes the only unknown and can be directly related to the voltage readout.

If the Seebeck coefficients are nearly constant across the targeted temperature range, the integral
in the above equation can be simplified, allowing one to solve directly for the temperature at the
probe tip,
In practice, vendors will provide calibration functions for their products. These functions are
usually high order polynomials and are calibrated with respect to a certain reference temperature,
e.g., 0 °C (32 °F). Suppose that the coefficients of the calibration polynomials are a0, a1, a2, ...,
an. The temperature at the probe tip can then be related to the voltage output as,

Note that the above formula is effective only if the reference temperature TRef in the experiment is
kept the same as the reference temperature specified on the data sheet. Furthermore, these
coefficients are unit sensitive. Make sure to use the vendor-specified temperature unit (i.e.
Celsius/centigrade, Fahrenheit, or Kelvin) when plugging in numbers.

Again, a thermocouple is a relative not absolute temperature sensor. In other words, a

thermocouple requires a reference of known temperature which is provided by ice water in the
above illustration. While ice water is an easy to obtain and well known reference, it is not
practical out side of a laboratory. Thus, common commercialized thermocouples often includes
another temperature sensor, such as thermistor, to provide the reading of the reference
(room/surrounding) temperature.

Thermoelectric Sensitivity

The Seebeck coefficients (thermoelectric sensitivities) of some common materials at 0 °C (32 °F)
are listed in the following table.

Seebeck Seebeck Seebeck

Material   Material   Material
Coeff. * Coeff. * Coeff. *
Aluminum 3.5   Gold 6.5   Rhodium 6.0
Antimony 47   Iron 19   Selenium 900
Bismuth -72   Lead 4.0   Silicon 440
Cadmium 7.5   Mercury 0.60   Silver 6.5
Carbon 3.0   Nichrome 25   Sodium -2.0
Constantan -35   Nickel -15   Tantalum 4.5
Copper 6.5   Platinum 0   Tellurium 500
Germanium 300   Potassium -9.0   Tungsten 7.5
*: Units are µV/°C; all data provided at a temperature of 0 °C (32 °F)
 
The above table also reveals some possible wire pairings. For instance, iron or copper can be put
on the positive terminal while constantan can be used for the negative terminal of a
thermocouple circuit (Type J and T).

Seebeck effect

Diagram of the circuit on which Seebeck discovered the Seebeck effect. A and B are two
different metals.

The Seebeck effect is the conversion of temperature differences directly into electricity and is
named for German physicist Thomas Johann Seebeck, who, in 1821 discovered that a compass
needle would be deflected by a closed loop formed by two metals joined in two places, with a
temperature difference between the junctions. This was because the metals responded differently
to the temperature difference, creating a current loop and a magnetic field. Seebeck did not
recognize there was an electric current involved, so he called the phenomenon the
thermomagnetic effect. Danish physicist Hans Christian Ørsted rectified the mistake and coined
the term "thermoelectricity". The voltage created by this effect is on the order of several
microvolts per kelvin difference. One such combination, copper-constantan, has a Seebeck
coefficient of 41 microvolts per kelvin at room temperature.[2]

The voltage V developed can be derived from:

where SA and SB are the thermopowers (Seebeck coefficient) of metals A and B as a function of
temperature and T1 and T2 are the temperatures of the two junctions. The Seebeck coefficients are
non-linear as a function of temperature, and depend on the conductors' absolute temperature,
material, and molecular structure. If the Seebeck coefficients are effectively constant for the
measured temperature range, the above formula can be approximated as:

The Seebeck effect is used in the thermocouple to measure a temperature difference; absolute
temperature may be found by setting one end to a known temperature. A metal of unknown
composition can be classified by its thermoelectric effect if a metallic probe of known
composition, kept at a constant temperature, is held in contact with it. Industrial quality control
instruments use this as thermoelectric alloy sorting to identify metal alloys. Thermocouples in
series form a thermopile, sometimes constructed in order to increase the output voltage, since the
voltage induced over each individual couple is small. Thermoelectric generators are used for
creating power from heat differentials and exploit this effect.

Thermopower

The thermopower or Seebeck coefficient, represented by S, of a material measures the magnitude

of an induced thermoelectric voltage in response to a temperature difference across that material,
and the entropy per charge carrier in the material. [3] S has units of V/K, though μV/K is more
common. Values in the hundreds of μV/K, regardless of sign, are typical of good thermoelectric
materials. The term "thermopower" is a misnomer since it does not measure power, but measures
the voltage induced in response to a temperature difference. An applied temperature difference
causes charged carriers in the material to diffuse from the hot side to the cold side. Mobile
charged carriers migrating to the cold side leave behind their oppositely charged nuclei at the hot
side thus giving rise to a thermoelectric voltage. Since a separation of charges creates an electric
potential, the buildup of charged carriers onto the cold side eventually ceases at some maximum
value since the electric field is at equilibrium. An increase in the temperature difference resumes
a buildup of charge carriers on the cold side, leading to an increase in the thermoelectric voltage,
and vice versa. The material's temperature and crystal structure influence S; typically metals have
small thermopowers because of half-filled bands caused by equal negative and positive charges
cancelling each other contributing to the induced thermoelectric voltage. In contrast,
semiconductors can be doped with excess electrons or holes, causing the magnitude of S to be
large. The sign of the thermopower determines which charged carriers dominate the electric
transport.[citation needed]

If the temperature difference ΔT between the two ends of a material is small, then the
thermopower of a material is defined approximately[4] as:

and a thermoelectric voltage of ΔV is seen at the terminals.

This can be written in relation to the electric field E and the temperature gradient by the
approximate[4] equation:

The absolute thermopower of the material of interest is rarely practically measured because
electrodes attached to a voltmeter must be placed onto the material in order to measure the
thermoelectric voltage, inducing a thermoelectric voltage across one leg of the measurement
electrodes. The measured thermopower then includes the thermopower of the material of interest
and the material of the measurement electrodes and is written as:

Superconductors have S = 0 since the charged carriers produce no entropy. This allows a direct
measurement of the absolute thermopower of the material of interest, since it is the thermopower
of the entire thermocouple. In addition, a measurement of the Thomson coefficient μ, of a

material yields the thermopower through the relation

S is an important material parameter that determines the efficiency of a thermoelectric material; a

larger induced thermoelectric voltage and a higher S mean a higher efficiency.

Charge-carrier diffusion

The Seebeck circuit configured as a thermoelectric cooler.

The same circuit configured as a generator.

The Seebeck effect is caused by two things: charge-carrier diffusion and phonon drag. Charge
carriers in the materials will diffuse when one end of a conductor is at a different temperature
than the other. Hot carriers diffuse from the hot end to the cold end, since there is a lower density
of hot carriers at the cold end of the conductor, and vice versa. If the conductor were left to reach
thermodynamic equilibrium, this process would result in heat being distributed evenly
throughout the conductor (see heat transfer). The movement of heat (in the form of hot charge
carriers) from one end to the other is a heat current and an electric current as charge carriers are
moving.

In a system where both ends are kept at a constant temperature difference, there is a constant
diffusion of carriers. If the rate of diffusion of hot and cold carriers in opposite directions is
equal, there is no net change in charge. The diffusing charges are scattered by impurities,
imperfections, and lattice vibrations or phonons. If the scattering is energy dependent, the hot
and cold carriers will diffuse at different rates, creating a higher density of carriers at one end of
the material and an electrostatic voltage.

This electric field opposes the uneven scattering of carriers, and an equilibrium is reached where
the net number of carriers diffusing in one direction is canceled by the net number of carriers
moving in the opposite direction. This means the thermopower of a material depends greatly on
impurities, imperfections, and structural changes that vary with temperature and electric field;
the thermopower of a material is a collection of many different effects.

Phonon drag

Phonons are not always in local thermal equilibrium; they move against the thermal gradient.
They lose momentum by interacting with electrons (or other carriers) and imperfections in the
crystal. If the phonon-electron interaction is predominant, the phonons will tend to push the
electrons to one end of the material, hence losing momentum and contributing to the
thermoelectric field. This contribution is most important in the temperature region where
phonon-electron scattering is predominant. This happens for
where θD is the Debye temperature. At lower temperatures there are fewer phonons available for
drag, and at higher temperatures they tend to lose momentum in phonon-phonon scattering
instead of phonon-electron scattering. This region of the thermopower-versus-temperature
function is highly variable under a magnetic field.[citation needed]

Peltier effect
The Peltier effect is the presence of heat at an electrified junction of two different metals and is
named for French physicist Jean-Charles Peltier, who discovered it in 1834. When a current is
made to flow through a junction made of materials A and B, heat is generated at the upper
junction at T2, and absorbed at the lower junction at T1. The Peltier heat absorbed by the lower
junction per unit time is equal to

where ΠAB is the Peltier coefficient for the thermocouple composed of materials A and B and Π A
(ΠB) is the Peltier coefficient of material A (B). Π varies with the material's temperature and its
specific composition: p-type silicon typically has a positive Peltier coefficient below ~550 K, but
n-type silicon is typically negative.

The Peltier coefficients represent how much heat current is carried per unit charge through a
given material. Since charge current must be continuous across a junction, the associated heat
flow will develop a discontinuity if ΠA and ΠB are different. Depending on the magnitude of the
current, heat must accumulate or deplete at the junction due to a non-zero divergence there
caused by the carriers attempting to return to the equilibrium that existed before the current was
applied by transferring energy from one connector to another. Individual couples can be
connected in series to enhance the effect. Thermoelectric heat pumps exploit this phenomenon,
as do thermoelectric cooling devices found in refrigerators.

Thomson effect
The Thomson effect was predicted and subsequently observed by Lord Kelvin in 1851. It
describes the heating or cooling of a current-carrying conductor with a temperature gradient.

Any current-carrying conductor (except for a superconductor) with a temperature difference

between two points either absorbs or emits heat, depending on the material. If a current density J
is passed through a homogeneous conductor, the heat production q per unit volume is:
where ρ is the resistivity of the material, dT/dx is the temperature gradient along the wire and μ is
the Thomson coefficient. The first term is the Joule heating, which does not change in sign; the
second term is the Thomson heating, which follows J changing sign.

Thomson relations

The Thomson coefficient is unique among the three main thermoelectric coefficients because it
is the only one directly measurable for individual materials. The Peltier and Seebeck coefficients
can only be determined for pairs of materials; hence, no direct methods exist for determining
absolute Seebeck or Peltier coefficients for an individual material. In 1854, Lord Kelvin found
relationships between the three coefficients, implying that only one could be considered unique.

The first Thomson relation is

where T is the absolute temperature, μ is the Thomson coefficient and S is the Seebeck
coefficient. The second Thomson relation is

where Π is the Peltier coefficient. It predicted the Thomson effect before it was formalized.

Figure of merit
The figure of merit Z for thermoelectric devices is defined as

where σ is the electrical conductivity, κ is the thermal conductivity, and S is the Seebeck
coefficient. The dimensionless figure of merit ZT is formed by multiplying Z with the average
temperature

A greater ZT indicates a greater thermodynamic efficiency, subject to certain provisions,

particularly that the two materials in the couple have similar Z. ZT is therefore a method for
comparing the potential efficiency of devices using different materials. Values of 1 are
considered good; values in the 3–4 range are essential for thermoelectrics to compete with
mechanical devices in efficiency. To date, the best reported ZT values are in the 2–3 range. [6][7][8]
Much of the research in thermoelectric materials has focused on increasing S and reducing κ by
manipulating the nanostructure of the materials.
Device efficiency
The efficiency of a thermoelectric device for electricity generation is given by η, defined as

The maximum efficiency ηmax is defined as

where TH is the temperature at the hot junction and T C is the temperature at the surface being
cooled. is the modified dimensionless figure of merit, which takes into consideration the
thermoelectric capacity of both thermoelectric materials being used in the device and is defined
as

where ρ is the electrical resistivity, is the average temperature between the hot and cold
surfaces and the subscripts n and p denote properties related to the n- and p-type semiconducting
thermoelectric materials, respectively. Since thermoelectric devices are heat engines, their
efficiency is limited by the Carnot efficiency, hence the TH and TC terms in ηmax. Regardless, the
coefficient of performance of current commercial thermoelectric refrigerators ranges from 0.3 to
0.6, one-sixth the value of traditional vapor-compression refrigerators.