Chapter 7

THERMOELECTRIC
THERMOMETRY

Thomson refers to this as the specific heat of electricity

because of an apparent analogy between and the usual
specific heat c of thermodynamics.
Note that represents the rate at which heat is absorbed , or
evolved , per unit temperature difference per unit current ,
whereas c represents the heat transfer per unit temperature
difference per unit mass .
The Thomson coefficient is also seen to represent an
emf per unit difference in temperature. Thus the total
Thomson voltage set up in a single conductor may be
expressed as

7.1 Historical Development of Basic Relations

Thomas Johann Seebeck , the German physicist , discovered
in 1821 the existence of thermoelectric currents while
observing electromagnetic effects associated with bismuthcopper and bismuth-antimony circuits [1],[2].
His experiments showed that , when the junctions of two
dissimilar metals forming a closed circuit are exposed to
different temperatures , a net thermal electromotive force is
generated that induces a continuous electric current .

The Seebeck effect concerns the net conversion of thermal

energy into electrical energy with the appearance of an electric
current.
The Seebeck voltage refers to the net thermal electromotive
force set up in a thermocouple under zero-current conditions.
The direction and magnitude of the Seebeck voltage E, depend
on the temperatures of the junctions and on the materials
making up the thermocouple.
For a particular combination of materials, A and B, and for
a small temperature difference, dt, the Seebeck voltage may be
written
dEs A, B dt

(7.1)

where A,Bis a coefficient of proportionality called the

Seebeck coefficient. (This is commonly called the
thermoelectric power).
Thus the Seebeck coefficient represents, for a given material
combination, the net change in thermal emf caused by a unit
temperature difference; that is ,
A, B

Es dEs
lim it

T 0 t
dt

(7.2)

Thus if

1
E at bt 2
2

determined by calibration,

then a bt 2 .

Note that, based on the validity of the experimental

relation,

t2

t2

t1

t1

Es dT dT dT

(7.11)

where t1 < t2 < t ,

It follows that is entirely independent of the reference
temperature employed .
In other words, for a given combination of materials, the
Seebeck coefficient is a function of temperature level only.

Jean Charles Athanase Peltier, the French physicist,

discovered in 1834 peculiar thermal effects when he introduced
small, external electric currents in Seebecks bismuthantimony thermocouple .
His experiments show that when a small electric current is
passed across the junction of two dissimilar metals in one
direction, the junction is cooled (i.e., it acts as a heat sink) and
thus absorbs heat from its surroundings.
When the direction of the current is reversed, the junction is
heated (i.e., it acts as a heat source) and thus releases heat to its
surroundings.

The Peltier effect concerns the reversible evolution, or

absorption, of heat that usually takes place when an electric
current crosses a junction between two dissimilar metals. (In
certain combinations of metals, at certain temperatures,
there are thermoelectric neutral points where no Peltier
effect is apparent).
This Peltier effect takes place whether the current is
introduced externally or is induced by the thermocouple
itself.
The Peltier heat was early found to be proportional to the
current and may be written

dQP Id

(7.12)

Where is a coefficient of proportionality known as the

Peltier coefficient or the Peltier voltage.
Note that represents the reversible heat that is absorbed,
or evolved, at the junction when unit current passes across
the junction in unit time, and that it has the dimensions of
voltage.
The direction and magnitude of the Peltier voltage
depend on the temperature of the junction and on the
materials making up the junction ; however at one
junction is independent of the temperature of the other
junction .

External heating, or cooling, of the junctions results in

the converse of the Peltier effect.
Even in the absence of all other thermoelectric effects,
when the temperature of one junction (the reference
junction) is held constant and the temperature of the other
junction is increased by external heating , a net electric
current will be induced in one direction .
If the temperature of the latter junction is reduced below
the reference junction temperature by external cooling, the
direction of the electric current will be reversed.
Thus the Peltier effect is seen to be closely related to the
Seebeck effect.

Peltier himself observed that, for a given electric current,

the rate of absorption, or liberation, of heat at a
thermoelectric junction depends on the Seebeck coefficient
a of the two materials.
Note that the Peltier thermal effects build up a potential
difference that opposes the thermoelectric current, thus
negating the perpetual-motion question.
William Thomson (Lord Kelvin), the English physicist,
came to the remarkable conclusion in 1851 that an electric
current produces different thermal effects, depending on the
direction of its passage from hot to cold, or from cold to hot,
in the same metal.

By applying the (then) new principles of thermodynamics

to the thermocouple and by disregarding (with tongue-incheek) the irreversible and conduction-heating processes,
Thomson reasoned that, if an electric current produced
only the reversible Peltier heating effects, the net Peltier
voltage would equal the Seebeck voltage and would be
linearly proportional to the temperature difference at the
junctions of the thermocouple .

This reasoning led to requirements at variance with

observed characteristics (i.e., dEs/dt constant).
Therefore, Thomson concluded that the net Peltier voltage
was not the only source of emf in a thermocouple circuit but
that the single conductor itself, whenever it is exposed to a
longitudinal temperature gradient, must also be a seat of
emf. A. C.
Becquerel had at that time already discovered a
thermoelectric neutral point, that is, Es = 0, for an
iron-copper couple at 280. Thomson agreed with
Becquerels conclusion and started his thermodynamic
reasoning from there.

The Thomson effect concerns the reversible evolution, or

absorption, of heat occurring whenever an electric current
traverses a single homogeneous conductor, across which a
temperature gradient is maintained, regardless of external
introduction of the current or its induction by the
thermocouple itself.
The Thomson heat absorbed, or generated, in a unit
volume of a conductor is proportional to the temperature
difference and to the current; that is,

dQT dT Id
T1

T2

(7.13)

where is a coefficient of proportionality called the

Thomson coefficient.

T2

ET dT
T1

(7.14)

where its direction and magnitude depend on temperature

level, temperature difference, and material considered.
Note that the Thomson voltage alone cannot sustain a
current in a single homogeneous conductor forming a closed
circuit, since equal and opposite emfs will be set up in the
two paths from heated to cooled parts.

Soon after his heuristic reasoning, Thomson succeeded in

demonstrating indirectly the existence of the predicted
Thomson emfs (see Figure 7. 1).
He sent an external electric current through a closed
circuit formed of a single homogeneous conductor that was
subjected to a temperature gradient and found the heat to be
slightly augmented or diminished by the reversible
Thomson heat in the paths from

Figure7.1 Thomson experiment to demonstrate existence

of reversible emfs in a single conductor.
(1) Points A and B can be found, when the switch is open,
having the same temperature.
(2)When an electric current is passed through the copper
bar, point A becomes cooler while point B becomes hotter.
(3) That is, Joule heating is slightly affected by the
reversible Thomson emf , which either opposes or adds to
the external emf when the copper bar is preferentially
heated.

(4) Thomson concluded that hot copper was electrically

positive with respect to cold copper, cold to hot or from hot
to cold, depending on the direction of the current and the
material under test.
In summary, thermoelectric currents may exist whenever
the junctions of a circuit formed of at least two dissimilar
materials are exposed to different temperatures.
This temperature difference is always accompanied by
irreversible Fourier heat conduction;
The passage of electric currents is always accompanied
by irreversible Joule heating effects.

At the same time, the passage of electric currents is

always accompanied by reversible Peltier heating or cooling
effects at the junctions of the dissimilar metals;
The combined temperature difference and passage of
electric current is always accompanied by reversible
Thomson heating or cooling effects along the conductors.
The two reversible heating-cooling effects are
manifestations of four distinct emfs that make up the net
Seebeck emf:
Es A, B t2 A, B t1 A dT B dT A, B dt (7.17)
where the three coefficients, ,, are related by the Kelvin
relations.

7.2 The Kelvin Relations

Assuming that the irreversible and heat-conduction
effects can be completely disregarded (actually, they can
only be minimized, since, if thermal conductivity is
decreased , electrical resistivity usually is increased, and
vice versa , see Figure 7.2) , the net rate of absorption of
heat required by the thermocouple to maintain equilibrium
in the presence of an electric current is
2
Qnet
q
1 2 ( A B )dT I Es I

(7.15)

This is in accord with the first law of

thermodynamics, according to which heat and work
are mutually convertible.
Thus the net heat absorbed must equal the electric
work accomplished or, in terms of a unit charge of
electricity, must equal the Seebeck emf Es, which
may be expressed in the differential form

dEs d ( A B )dT

(7.16)

The second law of thermodynamics may also be applied

to the thermocouple cycle (the unit charge of electricity
again being considered) as
S reversible

Q
Tabsolute

(7.18)

where Q represents the various components of the net

heat absorbed (i.e., the components of Es), and Tabsolute is
the temperature at which the heat is transferred across the
system boundaries.

Equation 7.10 can be expressed in the differential form

dS reversible

( A B )

d
dT 0
T
T

(7.19)

Combining the differential expressions for the first and

second laws of thermodynamics, we obtain the Kelvin
relations
dEs
(7.20)
A, B Tabsolute
Tabsolute A, B
dT
d 2 Es
( A B ) Tabsolute
2
dT

from which we can determine, ,, , when

Es is obtained as a function of T.

(7.21)

1 2
(7.22)
Es at bt L
2
is taken to represent the thermoelectric characteristic of a
thermocouple whose reference junction is maintained at
0 in which the coefficients a and b are obtained, for
example , by the curve fitting of calibration data , then
(a bt L )
Tabsolute (a bt L )
Tabsolute (b L )

(7.23)
(7.24)
(7.25)

An example of the use of these coefficients is given

in Figure 7.3.

Given the two constants, a and b, as determined with

respect to platinum,
Metal

a V/

b, V/

Iron(I)

+16.7

-0.0297

Copper(Cu)

+2.7

+0.0079

Constantan(C)

-34.6

-0.0558

By way of illustration, consider the following

combinations of materials: iron-copper and
iron-constantan, with their measuring junctions at
200 and their reference junctions at 0:

Iron copper
aI Cu aI aCu 16.7 2.7 14 V / o C
bI Cu bI bCu 0.0297 0.0079 0.0376 V / o C
Iron cons tan tan
aI Cu aI aCu 16.7 (34.6) 51.3V / o C
bI Cu bI bCu 0.0297 (0.0558) 0.0261V / o C

Since Seebeck voltage

1 2
Es at bt
2
Iron copper
1
Es 14(200) (0.0376)(200) 2
2
Es 2048V
Iron cons tan tan
1
Es 51.3(200) (0.0261)(200) 2
2
Es 10, 782V

Figure 7.3 Determination of various thermoelectric

quantities applied to thermocouples

Note how different combinations of materials give

widely different thermal emfs. Now we proceed to write
expressions for , and to note how the separate emfs
combine to give the ( net ) Seebeck emf. Since
Seebeck coefficient,

A, B a A, B b A, B T
Iron copper

0 14 (0.0376)(0) 14 V / o C
200 14 (0.0376)(200) 6048V / o C
Iron cons tan tan
0 51.3 0.0261(0) 51.3V / o C
200 51.3 0.0261(200) 56.52 V / o C

Note that it is the great difference in Seebeck coefficients

(thermoelectric powers) for the two combinations that
accounts for the difference in thermal emfs:
T

Es A, B dT
Since

TR

A,B Tabsolute A,B

=Peltier coefficient
=Peltier voltage

Iron copper
0 273(14) 3822V

200 473(6.48) 3065V

Iron-const an tan
0 273(51.3) 14, 005V
200 473(56.52) 26, 734V
Note that, in the case of the iron-copper ( I-Cu )
couple, cold hot , where as in the more usual I-C
couple, hot cold
.

Since A, B bA, BTabsolute

=Thomson coefficient ,

and

1
ET dT bA, B (TR2 T 2 )
2
TR

Thomson coefficient

Figure 7.3 continued

Iron copper
0.0376
ET
(2732 4732 ) 2805V
2
Iron cons tan tan
0.0261
ET
(2732 4732 ) 1947 V
2

We sum the various components

2

Es 2 1 dT SeebeckVoltage
1

Iron copper
Es 3065 3822 2805 2048V
Iron cons tan tan
Es 26, 734 14, 005 1947 10, 782 V

These figures, of course, check with the original

calculations. Note that, in the I-Cu case, the net Thomson
emf far outweighs in importance the net Peltier emf,
whereas in the I-C case , the converse is true .
Figure 7.3 (concluded)

7. 3 Microscopic Viewpoint of Thermoelectricity

What gives rise to these thermoelectric effects ? Recall
from your chemistry that when the loosely bound outer
(valence) electrons of a material absorb enough energy from
external sources, they may become essentially free from the
influence of their nuclei.
Once free, these electrons can absorb any amount of
energy supplied to them, and it is usual to suppose that the
free electrons in a metal act collectively as an idealized gas
(see Chapter2)
Even at a common temperature, however, the energies
and densities of the free electrons in different materials need
not be the same.

Thus when two different materials in thermal

equilibrium with each other are brought in contact, there
usually will be a tendency for electrons to diffuse across the
interface.
The electric potential of the material accepting electrons
would become more negative at the interface, whereas that
of the material emitting electrons would become more
positive. In other words, an electric field would be set up by
the electron displacement that opposes the osmotic process.
When the difference in potential across the interface just
balances the thermoelectric (diffusion) force, equilibrium
with respect to a transfer of electrons would be established.

If two different homogeneous materials are formed into

a closed circuit and the two junctions are maintained at the
same temperature, the resultant electric fields would
exactly oppose each other, and there would be no net
electron flow.
However, if these two junctions are maintained at
different temperatures , a net diffusion current will be
induced in coincidence with a net electric field (the
random motion of the free electrons is on the average in
the direction of the net potential gradient , and this gives
rise to the electric current).

From conservation principles, the power to drive this

electric current could only come from a net absorption of
thermal energy from the surroundings by the free
electrons of the materials, since there is no observable
change in the nature or composition of the thermoelectric
materials.
But what accounts for this net absorption of heat?
Why does the thermocouple act as a heat engine (i.e., a
device that makes available as work some portion of the
thermal energy acquired from a source)?

Consider first a closed circuit of a single material (thus

avoiding for a time the thermoelectric effects). Under the
influence of a temperature gradient alone, the material will
conduct a thermal current. But all the thermal energy
absorbed by the circuit at one zone is rejected by the circuit
at another zone.
Thus the Fourier effect exhibits no accumulation of heat
in the steady state, and cannot account for a thermally
induced electric current in a thermocouple circuit.
Again, under the influence of a voltage gradient alone,
this same single material closed circuit will con- duct an
electric current.

But the only thermal effect associated with this current is

the inevitable heat generation. Thus the Joule effect
exhibits no absorption of heat from outside the circuit and
cannot account for a thermally induced electric current in a
thermocouple circuit.
Evidently, when examining the mechanism by which a
closed circuit formed of two unlike materials acts as a heat
engine, we need concern ourselves only with the reversible
thermoelectric effects. (Perhaps similar reasoning guided
Thomson when he successfully obtained the valid Thomson
relations by intuitively disregarding the irreversible Joule
and Fourier processes.)

From this viewpoint, the resultant electric current in the

thermocouple circuit having its junctions maintained at
different temperatures agrees in direction with the natural
(Peltier) potential gradient at the hot junction , and thus
tends to wipe out ( do away with the need for ) this field .
At the cold junction, this same thermally induced
current must cross the interface against the natural
potential gradient, and this tends to build up a stronger
field of opposition there.

In terms of the idealized gas, the free electrons

expand isothermally across the hot junction interface
because the flow is in the direction of the Peltier
potential gradient there.
This expansion tends to cool the hot junction but, in
face of the isothermal restriction and in accord with the
first law of thermodynamics, the hot junction absorbs
just enough heat from its surroundings to maintain its
temperature.

These Peltier (junction) effects, although usually

predominating, do not tell the complete story. As
Thomson first pointed out, there will be thermoelectric
heating effects along each of the materials making up the
circuit whenever an electric current and a temperature
gradient exist.
The Thomson effect may be visualized as follows. If a
single conductor is preferentially heated, electrons
usually tend to leave the hot end more frequently than
the cold.
Just as we found at the junctions, an opposing electric
field would be set up along the single conductor by this
diffusion of electrons.

Thus whenever an electric current occurs in a closed

thermocouple circuit, it must either agree with or oppose
these Thomson (material) potential gradients, and this
accounts for heating and cooling effects in addition to the
Peltier (junction) effects discussed previously.
Hence the thermocouple in a temperature gradient does
qualify as a heat engine in that there will always be a net
absorption of heat from its surroundings per unit time , and
we see once more that it is just this excess of thermal power
arising entirely from reversible thermoelectric effects that
sustains the thermoelectric current in the circuit .

7 .4 Macroscopic Viewpoint of Thermoelectricity

The historical viewpoint presented thus far has avoided
the real irreversible I2R and heat conduction effects in
order to arrive at the useful and experimentally confirmed
Kelvin relations. We now discuss how the present-day
irreversible thermodynamic viewpoint removes this flaw
in our reasoning.

Basically, we judge whether a given process is

reversible or irreversible by noting the change in entropy
accompanying a given change in the thermodynamic
state. Thus, if ds Qq / Tabsolute , we say the process is
irreversible ; or , stated in a more useful manner ,
dS systerm dS across dS produced
boundary

or

inside

Qq
F
dS s dSo dSi

Tabsolute Tabsolute

(7.26)
(7.27)

Hence only in the absence of entropy within the system

boundaries do we have the reversible case,
,
dsreversible Qq / Tabsolute

which may be handled adequately by

classical thermodynamics in the steady and quasi-steady
states .
Evidently the rate of production of entropy per unit
volumeis an important quantity in irreversible
thermodynamics . It may be expressed as
1
F
1 dSi
(7.28)

Adx d

Adx
Tabsolute

where Adx is the area times the differential length.

Another significant quantity, the product

Tabsolute called the dissipation) , can always be split either
into two terms or into a sum of two terms , one associated
with a flow J, and the other associated with a force X.

Furthermore, in many simple cases a linear relation

is found (by experiment) to exist between the flow
and force terms so defined; for example, in the onedimensional, isothermal, steady flow of electric
charges, Qe / d , across a potential gradient-dE/dx , it
may be shown that

I dE
Tabsolute J e X e
A dx

(7.29)

where Je and Xe represent, respectively, the electric

flow and force terms, as defined by the entropy
production method. (D.G. Miller gives an excellent
review of the thermodynamic theory of irreversible
processes .
We follow his development closely. The term Je
represents the electric current density and the term Xe the
electric field strength or the electromotive force.
These are, of course, related by the linear Ohm's law
(i.e., Je = LeXe, where Le represents the electrical
conductivity).

Again, in the one-dimensional, steady flow of

thermal charges Qq / across
a temperature gradient
d
- dT/dx, it may be shown that
Q
Tabsolute
A

1
Tabsolute

dT
Jq X q
dx

(7.30)

where Jq and Xq represent, respectively, the thermal flow

and force, as defined by the entropy production method. The
term Jq represents the thermal current density, and the term
Xq represents the thermomotive force.
These are, of course, related by the linear Fouriers law
(i.e., Jq = LqXq where Lq represents the product of the
thermal conductivity and the absolute temperature).

It has been found that even in complex situations it may

always be stated that
Tabsolute J k X k

(7.31)

When several irreversible transport processes occur

simultaneously (e.g., the electric and thermal conduction in a
thermocouple), they will usually interfere with each other.
Therefore, the linear relations must be generalized to
include the various possible interaction terms.

Thus for the combined electric and thermal effects we

would write
J e Lee X e Leq X q

(7.32)

J p Lqe X e Lqq X q

(7.33)

Or, in general

J i Lij X j

(7.34)

We have just seen that an entropy production necessarily

accompanies both the and heat conduction effects (i.e., they
are irreversible); therefore, the Kelvin relations could not
follow from reversible thermodynamic theory without
certain intuitive assumptions.

By reasoning that the electric and thermal currents were

independent, Thomson tacitly assumed that Leq Lqe as
we shall show subsequently.
Experimentally, this reciprocal relationship was often
found to be true. The American chemist Lars Onsager
proved, in 1931, from a statistical-mechanics viewpoint,
that the assumption
(7.35)
Lij L ji
is always true when the linear relations between flows Jk
and forces Xk are valid . (For this work Onsager
subsequently was awarded a Nobel Prize.)
The Onsager reciprocal relation forms the basis of
irreversible thermodynamics .

By applying these concepts to the processes involved in

the thermocouple, we are led rationally and unambiguously
to the Kelvin relations .
Thus whenever the junctions of a thermocouple are
maintained at different temperatures, we expect that an
electric potential difference, an electric current, and a
thermal current will be present .
The dissipation for this thermoelectric process is simply
the sum of the electric and thermal terms previously given.
That is
I dE
Q
1 dT
Tabsolute

A dx
A Tabsolute dx

(7.36)

The generalized linear laws for this case have also been
given as
Leq dT
dE

J e Lee

Tabsolute dx
dT

(7.37)

Lqq dT
dE

J q Lqe

dT
T
dx

absolute

(7.38)

Recalling that the Seebeck emf is determined under

conditions of zero electric current, the Seebeck the
coefficientsmay be expressed in terms of the Onsager
coefficients as
Leq
dEs

dT I 0 LeeTabsolute

(7.39)

Recalling that the Peltier coefficient represents the heat

absorbed or evolved with the passage of an electric current
across an isothermal junction, this too may be expressed in
terms of the Onsager coefficients as
Lqe
J q

J e dT 0 Lee

(7.40)

Finally we recall that Thomson found experimentally (and

expressed in the Kelvin relations) that the Seebeck and
Peltier coefficients are related, Thus
dEs
Tabsolute

dT

I 0

(7.41)

In terms of the Onsager coefficients, this requires that

Lqe
Lee

Leq

Tabsolute

LeeTabsolute

(7.42)

which indicates that the experimental results agree with

those which are predicted by the entropy-production linearlaw Onsager reciprocal relation approach;

Lqe Leq

(7.43)

In other words, by irreversible thermodynamics, without

using any intuitive assumption. The Kelvin relations, also in
accord with experiment, must follow.

7.5 Laws of Thermoelectric Circuits

We have seen that, in 1821, T. J. Seebeck discovered
"thermomagnetism" when the junctions between two
different metals forming a closed circle were subjected to a
temperature difference.
Just a few years later, in 1826, A.C. Becquerel read a
paper to the Royal Academy of Sciences in Paris describing
the first recorded suggestion to make use of Seebecks
discovery as a means of measuring temperature.
It was not until 1885, however, that the problem of
measuring high temperatures was successfully attacked by
Henry LeChatelier.

He determined experimentally that the use of a platinum

wire against a platinum rhodium alloy wire gave the most
satisfactory "thermo-electric results . LeChateliers work is
still the basis of modern standard thermoelectric
thermometry.
Numerous investigations of thermoelectric circuits ,in
which accurate measurements were made of the current ,
resistance , and electromotive force have resulted in the
establishment of several basic laws.
These laws have been established experimentally beyond
a reasonable doubt and may be accepted in spite of any lack
of a theoretical development.

Law of Homogeneous Materials

A thermoelectric current cannot be sustained in a circuit
of a single homogeneous material however it varies in cross
section by the application of heat alone
A consequence of this law is that two different materials
are required for any thermocouple circuit.
Experiments have been reported suggesting that a
nonsymmetrical temperature gradient in a homogeneous
wire gives rise to a measurable thermoelectric emf.

A preponderance of evidence, however, indicates that any

emf observed in such a circuit arises from effects of local
inhomogeneities.
Furthermore, any current detected in such a circuit when
the wire is heated in any way whatever is taken as evidence
that the wire is inhomogeneous.

Law of Intermediate Materials

The algebraic sum of the thermoelectromotive forces in
a circuit composed of any number of dissimilar materials is
zero if all of the circuit is at a uniform temperature.
A consequence of this law is that a third homogeneous
material can always be added in a circuit with no effect on
the net emf of the circuit as long as its extremities are at
the same temperature.

Therefore, it is evident that a device for measuring the

thermo-electromotive force may be introduced into a circuit
at any point without affecting the resultant emf, provided all
of the junctions that are added to the circuit by introducing
the device are all at the same temperature.
It also follows that any junction whose temperature is
uniform and that makes good electrical contact does not
affect the emf of the thermoelectric circuit regardless of the
method employed in forming the junction (see Figure 7.4).

Figure 7.4 The emf is unaffected by the third material C

Another consequence of this law may be stated as

follows. If the thermal emfs of any two metals with respect
to a reference metal (such as C) are known, the emf of the
combination of the two metals is the algebraic sum of their
emfs against the reference metal (see Figure 7.5).

Law of Successive or Intermediate Temperature

If two dissimilar homogeneous materials produce a
thermal emf of E1: when the junctions are at temperatures
T1, and T2, and a thermal emf of E2 when the junctions are at
T2 and T3,the emf generated when the junctions are at T1 and
T3 will be E1 + E2 .

One consequence of this law permits a thermocouple

calibrated for a given reference temperature to be used with
any other reference temperature through the use of a
suitable correction (see Figure 7.6).
Another consequence of this law is that extension wires
having the same thermoelectric characteristics as those of
the thermocouple wires can be introduced in the
thermocouple circuit (say from region T2 to region T3 in
Figure 7.6) without affecting the net emf of the
thermocouple.

7.6 Elementary Thermoelectric Circuits

Two continuous, dissimilar thermocouple wires
extending from the measuring junction to the reference
junction, when used with copper connecting wires and a
potentiometer connected as shown in Figure 7.7, make up
the basic thermocouple circuit.
The ideal circuit given in Figure 7.8 is for use when
more than one thermocouple is involved. Note that each
thermocouple is made up of two continuous wires
between the measuring and reference junctions. This
circuit should be used for all precise work in
thermoelectric thermometry.

A circuit that requires only one reference junction is

known in Bureau of Standards publications as a zone-box
circuit. A diagram of one is shown in Figure 7.9.
Such a circuit should not be used when uncertainties
under 1F are required.
The usual thermocouple circuit, however, includes
measuring junctions, thermocouple extension wires,
reference junctions, copper connecting wires, a selector
switch, and a potentiometer, as indicated in Figure 7.10.
The uncertainties introduced by this circuit should be
expected to be greater than 1.

Many different circuit arrangements of these components

also are acceptable, depending on given circumstances, and
some are shown in Figure 7.11a, b, and c. These circuits can
be characterized briefly as follows:
a. Thermopile, for sensing average temperature level.
Advantages: magnifies thermoelectric power by the
number of couples in series, enabling the detection of small
changes in temperature level; one observation gives, by
calibration, the arithmetic mean of temperatures sensed by
N individual measuring junctions, when total emf is divided
by N.

Precautions: the emf may be too great for the indicator; a

short circuit may escape detection (giving erroneous
readings); this thermopile gives no indication of temperature
distribution; and the temperature / emf calibrations of all
couples must be identical.
b. Parallel arrangement, for sensing average temperature
level.
Advantage: one observation gives, by calibration, the
arithmetic mean of the temperatures sensed by N individual
measuring junctions.

Precautions: gives no indication of temperature

distribution; the temperature/emf calibrations of all couples
must be identical and linear; and all couples must have
equal resistances.
c. Thermopile, for sensing average temperature differences.
Advantages: the signal is magnified by the number of
couples in series ( permits detection of very small
temperature differences), and one observation, by
calibration , gives the arithmetic mean of the temperature
differences sensed by two groups of N measuring junctions
when the total emf is divided by N.

Precautions: temperature level is not indicated; a short

circuit may escape detection; and the temperature/emf
calibrations of all couples must be identical. A typical ice
bath is shown in Figure 7.12.
Various circuits for using potentiometers, compensated to
indicate temperature directly and uncompensated to indicate
voltages directly, are shown in Figure 7.13.

Grounded Thermocouple Circuits

Relatively little attention has been paid to electrical
effects that are extraneous to the basic thermocouple circuit.
Prime examples of external effects not always considered
are: effects of electrical and magnetic fields, cross-talk
effects, and effects connected with common mode voltage
rejection.
An excellent discussion of these noise effects in general
instrument circuits and of methods for reducing them is
given by Klipec . (On common mode voltage rejection see
also .) A brief review of these effects follows :

1. Electric fields radiated from voltage sources are

capacitively coupled to thermocouple extension wires and
cause an alternating noise signal to be superimposed on the
desired signal.
Electric noise is minimized by shielding the thermocouple
extension wire and grounding the shield.
2. Magnetic fields radiated from current-carrying
conductors produce noise current and hence noise voltage in
the thermocouple circuit. Magnetic noise is minimized by
twisting the thermocouple extension wires.

Adjacent pairs of a multipair cable tend to pick up noise

when pulsating d.c. signals are transmitted. Cross-talk
noise is minimized by shielding the individual pairs of
thermocouple extension wires.
4. Electrical connections made between a thermocouple and
a grounded instrument may introduce common mode
noise if different ground potentials exist along the wire
path.
Common mode noise is minimized by grounding the
thermocouple and its shielding at a single point as close
as practical to the measuring junction.
3.

Several arrangements of thermocouple/extension

wire/shield/ground combinations, acceptable from the noise
viewpoint, are shown in Figure 7.14.
It is evident from the foregoing that the grounding of
thermocouple circuits is an important consideration. It is a
fact that grounding is often done improperly.
It is shown in Section 7.9, under circuit analysis, that the
introduction of multiple grounds in a thermocouple circuit
can lead to serious temperature errors, errors that are over
and above those associated with thermoelectro-motive force
generation, with static and dynamic calibrations, with heat
transfer effects, and so on.

Circuits for Rotating Parts

Often in engineering the temperature of a rotating part
must be obtained. There are several methods for
accomplishing this task.
A rotating transformer may be used where in one coil
remains stationary while the other rotates, and hence the
signal is passed electrically from rotating to stationary parts.
Radio telemetry may be employed wherein a rotating
transmitter sends the temperature signal from a rotating
sensor to a stationary indicating device by means of a radio
frequency signal, antenna, and receiver system.

However, the most usual method is by a slip ring

arrangement wherein the electrical signal from a rotating
thermocouple is passed to the stationary world by means of
rotating slip rings and fixed brushes.
These three methods are illustrated in Figure 7.15. The
slip ring circuit that has proven to be useful for the highest
accuracy temperature measurement of a rotating part is
shown in Figure 7.16a.
This makes use of a separate rotating thermocouple to
sense the temperature in the zone where the necessary
transition takes place between the thermocouple wires from
the measuring junctions and the copper wires of the slip ring
assembly.

In Figure 7.16b, the accuracy of the basic slip ring

circuit is compromised through the built-in assumption
that a common temperature exists at both the rotating
and the fixed terminals of the slip ring assembly.
If this can be safely posited, or if the temperature
difference across the slip ring can be tolerated in the
overall measurement accuracy (e.g., a 2t across the
slip ring will introduce a 2error in the measurement),
the simplification of circuit b over a may be warranted.

A third arrangement, wherein the rotating zone

thermocouple of Figure 7.16a is replaced by a fixed zone
thermocouple extending into the slip ring assembly may
sometimes be used if it is felt that such a fixed zone
thermocouple adequately proclaims the temperature in the
rotating portion of the slip ring assembly.
A fourth arrangement, wherein a rotating resistance
thermometer (RTD, see Chapter 6) is used in place of any of
the above rotating or fixed zone thermocouple junctions,
can be used to advantage if it is important that copper wires
be used throughout the slip ring assembly .
A slip ring circuit is analyzed, thermoelectrically, in
Section 7.9.

7.7 Circuit Component Uncertainties

Typical uncertainties that can accompany the various
circuit components are discussed briefly below .

Measuring Junction
The junction of a thermocouple that is at the temperature
to be measured is referred to as the measuring junction.
Each measuring junction has its own peculiar
characteristics depending on such factors as materials,
methods of joining, age, and history of junction. Yet the
measuring uncertainties introduced by this junction are
small;
They are accounted for in the overall circuit calibration
(to be discussed), and do not introduce extraneous insidious
uncertainties in a temperature measurement.

Thermocouple Extension Wires

Extension wires are thermoelements inserted between the
measuring junction and the reference junction that have
approximately the same thermoelectric properties as the
thermocouple wire with which they are used (the A' and B'
wires of Figure 7.10).
The use of extension wires introduces at their extremities
at least four extraneous thermoelectric junctions in each
thermocouple circuit.

Even with normal usage, the resulting uncertainties can

amount to as much as, depending on the temperatures at the
ends of the extension wires, and on the particular wires
used.
Such large uncertainties can be minimized by calibrating
with given extension wires and then using the same wires in
the field, maintaining (as nearly as possible) the same
temperatures at their extremities in both circumstances.
These uncertainties can be entirely avoided by not
introducing any extension wires in the thermocouple proper.

Selector Switch
When placed in any circuit other than the basic circuit the
switch can introduce uncertainties of 1.5. It is not
enough to keep a switch at a uniform temperature, nor even
at a constant temperature.
To minimize uncertainties, the switch must be kept at the
same temperature in the field as it was during the
calibration. The uncertainties can be avoided entirely by
placing the switch in the copper extension Wires leading
from the reference junctions to the potentiometer.

Reference Junctions
The junction of a thermocouple that is maintained at a
known temperature is referred to as the reference junction.
In any but the basic circuit, reference junctions can
introduce uncertainties of 1.
These can be minimized by using the same reference
junction in the field as was used in the calibration.
The uncertainties can be avoided entirely by using a
proper thermocouple, that is, one for which the measuring
and reference junctions are simply the extremities of the
thermocouple wires.

Copper Connecting Wires

Copper wires used to connect the reference junctions of
a thermocouple to the switch or potentiometer are called
copper connecting wires.
These wires cause no uncertainty when they are used
between the reference junctions and the potentiometer

Potentiometer
A potentiometer is used to measure the emf generated
by the thermocouple. A standardized current is passed
through a wire of fixed resistance. The wire is calibrated
by marking the corresponding voltage drop along its
length.
Thus any unknown external emf (such as that
encountered in the thermocouple circuit) can be
compared with the known voltage drop along the
calibrated wire.

A sliding contact on the calibrated wire facilitates the

comparison, whereas a galvanometer indicates the balance
(null) condition by absence of needle deflection. With
reference to Figure 7.17, operation of the potentiometer is as
follows.
The switch is placed on (1), and the current from the
working cells is adjusted by rheostat C until the
galvanometer indicates the null. Under this condition the
current through the calibrated wire is "standardized."

The switch is then placed on (2), and the slide on the

calibrated wire is adjusted until the galvanometer again
indicates the balance condition.
The unknown voltage is now determined by the position
of the slide on the calibrated wire.
Since no current flows in the external circuit, the
resistance of that circuit introduces no error in the voltage
measurement.
An increase in external circuit resistance, however, does
decrease the sensitivity of the potential measurement.
This component introduces no uncertainty that is not
accounted for in the overall calibration.

7.8 Thermoelectric Reference Tables

Only a few of the large number of possible
combinations of materials are actually used in
thermoelectric thermometry.
These are chosen on the basis of their standing in the
Thermoelectric Series, their Seebeck coefficients (i.e.,
thermoelectric powers), and on their stability and
reproducibility as evidenced by the establishment of
Thermocouple Reference Tables. In the following
section, these three tabulations are presented.

Thermoelectric Series
The various conductors have been tabulated in an order
such that, at a specified temperature, each material in the list
is thermoelectrically negative with respect to all above it
and positive with respect to all below it (see Table 7.1).
Although this tabulation resembles the electrochemical
electromotive force series, the position of a material in one
series bears no relation to that in the other.

Seebeck Coefficients
Nominal thermoelectric powers of various
thermoelements with respect to Platinum 67 (a standard
maintained at the NBS), and of various common
thermocouple types, are presented in Tables 7.2 and 7.3.
These are quite useful in the analysis of circuits such as
those dealt with in Section 7.9. Curves to present this same
information graphically are given in Figures 7.18 and 7.19.

Thermocouple Reference Tables

Thermocouple reference values represent in both form and
magnitude the nominal characteristics of particular
thermocouple types.
Thermocouple wires are carefully selected and matched to
conform with these tables within prescribed limits. The
printed scales of all direct temperature-indicating
potentiometers are based on such tables.
Calibration curves, in the form of voltage -or
temperature-difference plots, are obtained by comparing
calibration data with reference values

A satisfactory table of reference values for use with

thermocouples must be capable of easy and unique
generation for a number of reasons:
(1) the values are used by many people;
(2) their storage in computer applications must not present a
problem; and
(3) since interpolation must be used, unique values at all
arbitrary points must be available.
The last requirement means that a mathematically
continuous functional relation must exist between the
temperatures and voltages with which the table is
concerned.

Satisfactory reference values must also agree closely with

the characteristic of the thermocouple type being considered
so that differences in values change slowly and smoothly.
The established reference tables adequately fulfill all these
requirements. Unique polynomials are available for
generating tables for each of the seven thermocouples now
in common use.
These are given in Tables 7.4 and 7.5 for easy reference.
A short discussion of each thermocouple type follows .

TYPE T (copper / constantan).

This type can be represented by an eighth-degree equation
as in Table 7.4a. This is used to generate exact values of
voltage as a function of temperature from 0 to 400.
The inverse relation, for temperature as a function of
voltage, is generated over the same temperature range by
another polynomial also given in the table.
This procedure is necessarily inexact, but will yield
reference temperatures to within known uncertainty bands.
For type T, temperatures are given to 0.2 from 0 to
400 .

TYPE J (iron/constantan).
Output of this type can be determined as a function of
temperature from by a seventh-degree equation in Table
7.4b.
The resulting values are exact by definition. This shows
the inverse relation for temperature as a function of voltage
over the same temperature range. For type J, temperatures
are given to 0.1 from 0 to 760.

TYPE E (chromel /constantan).

Thermocouples of this type can be represented by a ninthdegree polynomial as in Table 7.4c.
Voltage generated as a function of temperature from 0
to 1000 can be calculated, as can temperature as a
function of voltage using the inverse relationship . For the
latter case , temperatures are given to 0.1 from 0 to
1000 .

TYPE K (chromel / alumel).

Outputs of these thermocouples can be represented by the
equation in Table 7.4d.
An eighth -degree equation with an exponential term is
used to generate values of voltage as a function of
temperature from 0 to 1372. The inverse relation
provides reference temperatures accurate to 0.02 from
400to 1100.
TYPE B (platinum-30% rhodium / platinum).
An eighth-degree equation, given in table 7.5a is used to
generate these voltages as a function of temperature from
0 to 1820.

Type R (platinum-13% rhodium / platinum).

Two third-degree equations are required to generate
voltage as a function of temperature from 630 to 1665,
as shown in Table 7.5b.
TYPE S (platinum-10% rhodium / platinum).
From the antimony point to the gold point, that is, from
630.74 to 1064.43, a second-degree equation is used to
generate voltages for this type thermocouple. From 1064
to 1665 , a third-degree equation is used. The required
coefficients of these polynomials are given in Table 7.5c.

A table generated by the polynomials given in Tables 7.4

and 7.5, for six of the most commonly used types of
thermocouples, is presented as Table 7.6. Prior to the
publication of the NBS polynomials of Tables 7.4 and 7.5,
there was no unique , internationally accepted, mathematical
generation scheme available that would reproduce the
established thermocouple reference table values .

One method that found wide acceptance in the ISA ,

ASME , ASTM , and industry in general , was based on the
trial-and-error establishment of a few key values of voltage
and temperature and a series of equations of specified
degree to interpolate voltages between the key points .
Today this generation scheme is no longer required and is
only of historical interest. NBS Monograph 125[29] is the
accepted standard for the nominal characteristic for all
conventional thermocouple types.

7.9 Thermoelectric Circuit Analysis

An important phase of each temperature measurement by
means of thermocouples is the thermoelectric circuit
analysis. This operation can be systematized by observing
the following set of rules.
1. Draw an equivalent circuit, numbering all
thermoelectric junctions, and show an assumed direction of
current.
2. Indicate the direction of the potential drop at each
junction, guided by the outputs of each material with respect
to platinum-67 (see Figure 7.18).

3. Compute the net emf in terms of the potentials at each

junction (assigning a plus sign if the potential drop is in the
same direction as the assumed current).
4. Combine the voltages algebraically to a form that
allows easy reference table look-up (i.e., combine in terms
of usual thermocouple combinations).
5. Compute the errors.
The examples that follow illustrate the application of
these rules, and have been chosen to represent common and
yet serious thermocouple circuit errors.

Example 1.
Use of Incorrect Extension Wires. A chromel-alumel (ChAl) thermocouple was connected by mistake with ironconstantan (I-C) extension wires to a potentiometer in such
a manner that the output emf was on scale.
The actual temperatures were at measuring junction
TM 60; at reference junction TR 32; and at the
junction between the thermocouple and extension wires
TJ 130. What was the error in the measurement?
1. Draw an equivalent circuit (see Figure7.20).
2. Indicate direction of all potential drops (dotted arrows
in Figure 7.20)
3,4. Compute net emf:

Enet E1 E2 E3 E4
E1 (Ch A1)60o F 0.619mV
E2 (Ch C )130o F 3.329mV
E3 ( I C )32o F 0mV
E4 ( I A1)130o F (ch A1)130o F (Ch C )130o F ( I C )130o F
2.206 3.329 2.820mV
1.697 mV ( seeFigure7.21)
Enet 0.619 3.329 0 1.697 4.407mV

whereas the correct emf should have been:

E (Ch Al )60oF
(Ch Al )32oF 0.619mV

5. Compute errors
net voltage error =4.407-0.619=3.788mV
net voltage error =225 60 165oF, (on Ch A1scale)
net voltage error =183 60 123oF, (on I Cscale)

It goes without saying that, on either thermocouple scale,

errors of this magnitude cannot be tolerated.

Example 2.
Use of Incorrect Polarity Wires. The extension wires of a
chromel-alumel
thermocouple
were
inadvertently
interchanged. The actual temperatures were at measuring
junction TM 980; at reference junction TR
32; and at the junction between the thermocouple and
extension wires TJ 100.
What was the error in the measurement?

1, 2. Draw an equivalent circuit (see Figure 7.20).

3, 4. Compute net emf:
Enet E1 E2 E3 E4
E1 (Ch A1)60o F 0.619mV
E2 (Ch C )130o F 3.329mV
E3 ( I C )32o F 0mV
E4 ( I A1)130o F (ch A1)130o F (Ch C )130o F ( I C )130o F
2.206 3.329 2.820mV
1.697 mV ( seeFigure7.21)
Enet 0.619 3.329 0 1.697 4.407mV

whereas the correct emf should have been

E (Ch A1)980o F (Ch A1)32o F 21.777mV

5. Compute errors
net voltage error =26.637-7.958=18.679mV
net temperature error =700-255 445oF

Once again, a most common thermocouple circuit error,

namely interchanging extension wires, is seen to lead to a
very serious temperature measuring error.

Example 3.
Use of Improper Grounding. A chromel-constantan
thermocouple, grounded at its measuring junction according
to Figure 7.14, was inadvertently grounded at its reference
junction also. The actual temperatures were: at measuring
junction, TM = 700; at reference junction, TR =32.
What is the predicted error in the measurement?

1. Draw an equivalent circuit:

Figure7.22 illustrates the multigrounded circuit under
consideration. Figure7.23 depicts the equivalent circuit that
represents the multigrounded thermocouple.
2. In this example, the direction of all potential drops is
indicated by electrical cell symbols, where the drop is from
minus to plus at the junction.
3, 4. Compute net emf: A voltage summation is written
around the outer ground loop to obtain the current in the
loop as follows.
E ( E pq )M iRg iRn ( E pn )M 0
(7.44)

Where Epg M signifies the emf set up by the

positive thermoelement and the ground wire at the
measuring junction temperature , and so on . Thus

where Epg M signifies the emf set up by the positive

thermoelement and the ground wire at the measuring
junction temperature , and so on . Thus
( E pn ) M ( E pg ) M
i
Rg Rn

(7.45)

Note that chromel is the positive element with respect to

constantan and that copper is assumed to be the grounding
wire.
Given the ground loop current, the net voltage set up by
the doubly grounded thermocouple circuit can be
determined as follows.

Enet iRg ( E pg ) M iRn ( E pn ) M

The pertinent resistance values are:
for constantan Rn 2.902
Rg 0.0646
for copper

(7.46)

The pertinent voltage values are:

( E pn ) M ( ECh C ) 700o F 26.637 mV
( E pg ) M ( ECh Cu )700o F ( ECh C ECu C ) 700o F
( E pg ) M 26.637 19.095 7.542mV
26.637 7.542
6.437mV
0.0646 2.902
Enet iRg ( E pg ) M 6.437(0.0646) 7.542 7.958mV

5. The temperature error for this doubly grounded

thermocouple can be estimated as follows
net voltage error =26.637-7.958=18.679mV
net temperature error =700-255 445oF

This error is obviously much larger than any other error

associated with thermocouple
. circuits, and it is clear that
doubly grounded thermocouple circuits are to be avoided at
all costs.

Example 4.
Rotating thermocouple circuit analysis. A rotating ironconstantan thermocouple is connected through a slip ring to
a stationary potentiometer and reference junction.
The unknown temperature at the transition between the
thermocouple wires and the copper slip ring wires is
accounted for by a special rotating iron-constantan
thermocouple connected as shown in Figure 7.16a.
The actual temperatures were: at measuring junction
TM 500; at reference junction TR 32; and at the
slip ring, TJ=150.What was the error in the measurement?

1, 2. Draw an equivalent circuit (see Figure7 .24

.
3, 4. Compute net emf:
Enet E1 E2 E3 E4

E1 (Ch A1)980o F 21.777mV

E2 (Ch A1)100o F 1.520mV
E3 (Ch A1)32o F 0mV
E4 (Ch A1)100o F 1.520
Enet 21.777 1.520 0 1.520 18.737 mV

Since this is the voltage required, there are no circuit errors

in this example.