Lab Practicum Part 2

Chapter I 3
Chapter I pressure P multiplied by the piston area S . The work done by the gas
equals δA = F ∆x = P S∆x = P ∆V , where ∆x is the piston displa ement
THERMODYNAMIC PROCESSES and ∆V = S∆x is the in rement of the gas volume. To maintain the pressure
onstant the displa ement must be small ompared to the ylinder length
and so slow that a pressure gradient is negligible. To this end the piston
velo ity should be mu h less than the speed of sound in the gas. Su h an
expansion is reversible, i.e. no hange in the ylinder environment ould be
dete ted when the piston returns to its initial position.
Let us write the work done by the gas via innitesimally small quantities:
δA = P dV. (1.3)
The rst law of thermodynami s. The law of onservation of energy A ording to equation of state gas pressure depends not only on its volume
states that a heat Q obtained by a thermodynami system is shared between but also on gas temperature. To integrate Eq. (1.3) one must know how
the in rease in the system's internal energy ∆U and the work A performed the temperature varies with volume during the whole pro ess, information
by the system over external obje ts: about initial and nal states is not enough.
Substituting Eq. (1.3) into the rst law of thermodynami s one obtains:
Q = ∆U + A. (1.1)
Equation (1.1) is the mathemati al statement of the rst law of thermody- δQ = dU + P dV. (1.4)
nami s. This equation provides the thermodynami denition of internal
energy and the way to measure it: a hange in internal energy of a system This equation is also valid for liquids. For solids sometimes it is ne essary
is equal to the work done by external for es providing no heat has been to take into a ount the work due to shear deformations.
transferred to the system (adiabati pro ess). Internal energy in ludes
kineti and potential energy of mole ules and the energy of intera tions
Heat apa ity. The ratio of the heat δQ absorbed by a body during some
pro ess ¾x¿ to the in rement of the body temperature dT is alled the heat
between the mole ules.
apa ity of the body:
In terms of innitesimals Eq. (1.1) be omes
δQ
C= . (1.5)
δQ = dU + δA. (1.2) ∂T x
Sin e internal energy U is a fun tion of system state the innitesimal Usually heat apa ity is referred to a unit mass of the body (spe i
in rement of internal energy is written as dierential dU ; the in rement of heat apa ity) or to one mole (molar heat apa ity). Sometimes the spe i
heat δQ and work δA is written using a dierent symbol δ (delta) to stress heat is denoted by small c and the molar heat apa ity by the apital C .
that they are not dierentials of a fun tion of state. In order to integrate the To avoid onfusion it is re ommended to indi ate expli itly whi h apa ity
heat and the work one has to know the pro ess between the initial and nal is used. It is also important that heat apa ity depends on the pro ess sin e
states be ause the result of integration depends on the whole pro ess rather the heat obtained an be partially onverted to work. In some pro esses the
than on the initial and nal states. The result of integration of internal work an be so large that the heat apa ity be omes negative, i.e. the body
energy depends only on the initial and nal states of the system: temperature drops despite the heat transfer.
Z
Let us onsider the energy of a body to be a fun tion of body volume
dU = U2 − U1 .
and temperature, U = U (T,V ), and substitute its dierential
Work done by gas. Consider expansion of a gas

ontained in a ylinder ∂U ∂U
under a movable piston. The for e F exerted on the piston equals the dU = dT + dV
∂T V ∂V T
4 THERMODYNAMIC PROCESSES Chapter I 5
into the rst law of thermodynami s: Assume that U = U (T, V ). Then

∂U ∂U 1 ∂U 1 ∂U
δQ = dU + δA = dT + dV + P dV = dS = dT + + P dV.
∂T V ∂V T T ∂T V T ∂V T
" #
∂U ∂U
= dT + P + dV. Sin e dS is exa t dierential, the last relation gives
∂T V ∂V T

∂ 1 ∂U ∂ 1 ∂U
Dividing this relation by dT one obtains heat apa ity Cx of the pro ess = +P .
∂V T ∂T V ∂T T ∂V T
¾x¿: " #
∂U ∂V A bit of algebra gives the desired formula
Cx = Cv + P + . (1.6)
∂V T ∂T x
∂U ∂P
The derivative (∂V /∂T )x is al ulated for the parti ular pro ess ¾x¿, e.g. =T − P. (1.9)
∂V T ∂T V
at onstant volume (x = V ), pressure (x = P ), or other restri tion. The
quantity Cv = (∂U/∂T )V in Eq. (1.6) is heat apa ity at onstant volume.
To determine heat apa ity by means of Eq. (1.6) one must know the Heat apa ity of ideal gas. Substitution of equation of state of ideal
equation of state of the body, i.e. the fun tion P = P (T,V ), and the gas P V = RT into Eq. (1.9) shows that internal energy of ideal gas is
dependen e of the internal energy on temperature and volume, U = U (T,V ). independent of its volume:
If the equation of state is known the dependen e of heat apa ity on volume ∂U
= 0.
an be derived by means of the se ond law of thermodynami s. ∂V T
The se ond law of thermodynami s. The se ond law of thermodynami s Equation (1.6) for ideal gas is simplied:
determines the dire tion of evolution of physi al pro esses and for reversible
pro esses the law allows one to derive various relations between physi al ∂V
Cx = Cv + P . (1.10)
quantities. ∂T x
There are several denitions of the se ond law. The following mathemati al
Using this formula and equation of state of ideal gas one obtains the
denition is espe ially suited for the purpose of derivation of quantitative
following relation between heat apa ity at onstant volume Cv and heat
relations. The denition onsists of two statements:
apa ity at onstant pressure Cp (Mayer's relation))1 :
1. There is a fun tion of the system state alled entropy.
2. Entropy always grows during a real irreversible pro ess. Cp − Cv = R. (1.11)
A pro ess is reversible if regardless of the dire tion of the pro ess
(forward or ba kward), the environment remains undisturbed when the The ratio of these heat apa ities is alled adiabati index (it is often
system returns to initial state. For su h a pro ess an innitesimal in rement used in various appli ations):
of entropy dS is related to the innitesimal heat obtained by the system as:
Cp
δQ γ= . (1.12)
dS = . (1.7) Cv
T
1 For any substan e the dieren e C − C is determined by the equation of state
Substituting δQ into the rst law of thermodynami s (1.2) one obtains the p v
P (T, V ) and it is independent of the fun tion U (T, V ). This follows from the relation
relation between the dierentials be ause entropy is a fun tion of state and whi h is obtained by substitution of Eq. (1.9) into Eq. (1.6):
therefore independent of any reversible pro ess:
∂P

∂V

Cp − Cv = T .
1 P ∂T V ∂T P
dS = dU + dV. (1.8)
T T
In general ase Cv is temperature dependent but usually it is onsidered example, the heat apa ity of mole ular hydrogen orresponds to that of
approximately onstant, so that internal energy of gas is proportional monoatomi gas at temperatures below 100 K.
to its temperature. This orresponds to the ideal gas omposed of solid In addition to translational and rotational degrees of freedom the
non-intera ting parti les. A ording to equipartition theorem of statisti al mole ules also have vibrational ones, but in gases the vibrations are usually
physi s ea h degree of freedom of a parti le arries the average energy of ex ited at temperatures signi antly above the room temperature. At high
kT /2, where k = 1.38 · 10−23 J/K = 1.38 · 10−16 erg/K is the Boltzmann temperatures mole ules disso iate and be ause of that the vibrations are
onstant. The equipartition theorem is proved in the framework of lassi al not ex ited to the degree when the equipartition theorem an be applied
(non-quantum) me hani s. (hydrogen is an ex eption).
If the number of degrees of freedom per parti le is i 2 then the energy
per parti le is ikT /2. The internal energy U and heat apa ity Cv per mole Adiabati pro ess. If during a pro ess there is no heat ex hange between
are, respe tively: the system and the environment the pro ess is alled adiabati . Let us derive
an equation of a quasistati adiabati pro ess for an ideal gas whi h energy
i i i is independent of its volume.
U= kNA T = RT ; Cv = R,
2 2 2 Using the rst law of thermodynami s (1.4), setting δQ = 0, and
substituting dU = Cv dT one obtains
where R = 8.31 J/(mol·K) = 8.31 · 107 erg/(mol·K) is the gas onstant,
NA = 6.02 · 1023 mol−1 is the number of mole ules per mole (the Avogadro Cv dT + P dV = 0.
onstant).
A ording to Eq. (1.12) the adiabati index is The pressure P an be ex luded with the aid of the equation of state P V =
= RT :
i+2 dT dV
γ= . (1.13) CV +R = 0.
i T V
A monoatomi gas has three translational degrees of freedom, so i = 3 The equation is easily integrated if Cv is onstant (whi h orresponds to the
and γ = 5/3 = 1.666. The experimental values for helium and neon are lassi al theory of heat apa ity):
γ = 1.66 and γ = 1.64, respe tively, whi h agrees with the theory.
A diatomi gas at room temperature has two rotational degrees of T V R/Cv = T V γ−1 = const. (1.14)
freedom in addition to the translational ones, so i = 5 and γ = 7/5 = 1.4.
The experimental values for hydrogen, nitrogen, and oxygen are γ = 1.41, This is an equation of adiabati pro ess in the variables T , V . Let us rewrite
γ = 1.404, and γ = 1.401, respe tively, i.e. quite lose to the theoreti al it in the variables P , V . Using again the equation of state P V = RT and
value. Mayer's relation (1.11) one gets an equation
Multiatomi gases also exhibit a good agreement with the theory. The
mole ules have three translational and three rotational degrees of freedom, P V γ = const. (1.15)
orresponding to rotations around three independent axes, therefore i =
= 6 (vibrational degrees of freedom are not usually ex ited at room Here γ = Cp /Cv is the adiabati index (1.12), (1.13) whi h plays an
temperatures). For water vapors (H2 O) γ = 1.32, for methane (CH4 ) γ = important role in theoreti al des ription of adiabati pro esses. An example
= 1.31. The orresponding theoreti al value is γ = 4/3 = 1.333. is propagation of sound. The Bernoulli's equation of ompressible gas
The lassi al theory of heat apa ity does not always agree with in ludes the adiabati index whi h determines, in parti ular, a kind of
experiment. In a wide range of temperatures heat apa ity varies signi antly, motion (soni or supersoni ) of the gas.
this is due to quantum ee ts. The number of degrees of freedom is less at
low temperatures be ause rotational degrees of freedom are not ex ited. For
Polytropi pro ess. A pro ess in whi h heat apa ity C remains onstant
is alled polytropi . Let us onsider an ideal gas with temperature independent
2 i is the number of independent oordinates spe ifying the body's position. heat apa ity Cv and derive the equation of polytropi pro ess. Repla ing
the pressure in Eq. (1.10) with that of ideal gas and then using Eq. (1.12) Mole ules of real gases intera t, at lose range the intera tion is repulsion
one obtains: and at large distan e it is attra tion. A simple equation of state whi h
RT dV R dV dT a ounts for intera tion between mole ules is van der Waals equation:
C = Cv + , = .
V dT C − Cv V T a
C − Cp Cp − nCv P + 2 (V − b) = RT. (1.18)
T V n−1 = const, P V n = const, n = , C= . V
C − Cv 1−n
Here a and b are parameters onsidered as onstants. Equation (1.18) is
This equation be omes the equation of adiabati pro ess (1.15) at C = 0 written for one mole of gas, the equation for ν moles has V /ν instead of V .
and equation of isothermal pro ess P V = const in the limit C = ±∞, The ratio a/V 2 a ounts for the redu tion in pressure be ause of
respe tively. attra tion between mole ules. The pressure exerted on some small area is
Speed of sound. Propagation of sound in a gas is adiabati pro ess. proportional to the density of mole ules in the proximity of the area, so
Compression and de ompression alternate so qui kly that heat ex hange the redu tion in pressure due to the attra tion is proportional to the same
between layers of gas with dierent temperatures does not happen. The quantity. Therefore the redu tion in pressure is proportional to the square
speed of sound an be found from the equation of adiabati pro ess by using of the density of mole ules, i.e. inversely proportional to the square of molar
the general formula: volume.
s This on lusion is independent of the exponent n in the expression
dP for the for e between mole ules, f ∼ 1/rn (here r is the separation
c= . (1.16)
dρ between mole ules). However, onvergen e of the integral whi h sums up
the mole ular for es requires the for e to de ay with distan e faster than
Taking logarithm and then dierentiating equation P V γ = const one
1/r3 , i.e. the exponent n must be greater than 3.
obtains:
dP dV dP P The attra tion for e at large distan e is ele trostati in nature. Atoms
+γ =0 or = −γ . and mole ules are ele tri ally neutral, however the distributions of opposite
P V dV V
harges in a mole ule are not identi al, whi h results in an ele tri eld
Then the relation between spe i volume and density, ρv = 1, gives
around a mole ule. The eld polarizes the nearby mole ules and this leads
dV V to the attra tion.
dρ
=− .
ρ A ording to Coulomb's law the for e between two harges is inversely
proportional to the distan e squared. A al ulation based on Coulomb's
Combining the two relations one obtains the speed of sound as: law shows that the for e between two ¾rigid¿ dipoles, in whi h the relative
distribution of harges is xed, is inversely proportional to the forth power
c2 =
dP
=
dP dV P V
=γ ·
P
=γ =γ
RT of the distan e, while for a dipole indu ed by polarization ee ts the for e
dρ dV dρ V ρ ρ µ de ays even faster. Thus the ondition n > 3 holds for neutral atoms and
mole ules.
or s The parameter b spe ies the minimum volume, whi h one mole of a
RT substan e o upies at large pressure, when the mole ules are pa ked as lose
c= γ , (1.17)
µ as possible. The parameter b is of the same order of magnitude as the molar
volume of liquid at a temperature whi h is su iently lower than the riti al
where µ is the molar mass of the gas.
temperature. For example, b = 30 m3 /mol for water while the molar volume
Van der Waals equation. The equation of state P V = RT approximates at the standard onditions is 18 m3 /mole.
the equation of state of a real gas at low densities and high temperatures. By denition the parameters a and b are onstants. However experiment
At large density and su iently low temperature any gas an be liqueed, shows that the parameters depend on temperature and density.
whi h would be impossible if the ideal equation were exa t. In order to avoid possible ambiguities the numeri al values of the
P
parameters given in manuals orrespond to the values obtained at the riti al A1
point. Eqs. (1.19) explain the orresponden e.
Thus van der Waals equation is a simple relation approximating the
equation of state of a real gas only in a limited range of thermodynami
parameters. To des ribe the properties of real gases better more sophisti ated
equations of states are used.
P r K
The main properties of van der Waals equation an be onveniently

studied on the P − V diagram where the isotherms are plotted (see Fig. 1.1). D
Note the isotherm passing through the riti al point ¾K ¿ determined by A M
B
the onditions: 2 B1
∂P ∂ P
= 0 and = 0. C
∂V T ∂V 2 T
Using van der Waals equation one obtains: V r 2V r 3V r V
Fig. 1.1. Isotherms of van der Waals equation
8a a
Vc = 3b, Tc = , Pc = . (1.19)
27Rb 27b2
and liquid is νl and νg , respe tively. Then, using VA = Vl and VB = Vg , one
Consider the isotherm A1 B1 whi h segments shown by the dashed obtains:
lines orrespond to metastable states: AC is superheated liquid and DB is
(νl + νg )VM = νl Vl + νg Vg ;
super ooled gas. Su h states are used in a bubble hamber and Wilson
hamber to dete t parti les. The dotted line CD orresponds to an unstable νg mg VM − Vl AM
state. On this line the quantity (∂P/∂V )T > 0, so su h a state does not = = = . (1.20)
νl ml Vg − VM MB
exist.
The part of the isotherm orresponding to metastable and unstable states Let us give a more detailed derivation of Eq. (1.20). At an arbitrary point
must be orre ted. The line ACDB should be repla ed with the horizontal M on the line AB the net volume VM of the double-phase uid onsists of
line AB drawn in a ordan e with the rule proposed by Maxwell: the areas the volume of liquid (Vl )M and the volume of gas (Vg )M :
onned between the line and the isotherm below and above the line must be
equal. To justify the rule noti e that the net heat transfer during the pro ess VM = (Vl )M + (Vg )M . (1.21)
going around a losed loop omposed of isotherms of the same temperature
must be zero (the Clausius theorem). Therefore the work done during the Now,
pro ess must vanish and so does the area on the P − V diagram. (ml )M (mg )M
(Vl )M = , (Vg )M = . (1.22)
The boundary of the region of double-phase states is shown by thin line ρl ρg
AKB . On the left and the right to the boundary there are liquid and gas, The masses of liquid and gas vary along the line AB , but their densities
respe tively. Within the boundary the phases oexist and the mass of ea h remain the same be ause the pressure and the temperature are onstant.
phase at a parti ular point of the diagram is inversely proportional to the Let us express the densities ρl and ρg in terms of the volumes VA = Vl and
horizontal distan e between the point and the orresponding boundary. Let VB = Vg :
us give the proof. ml + mg ml + mg
As it was already mentioned, the volume V in van der Waals equation ρl = , ρg = . (1.23)
Vl Vg
orresponds to one mole, so νV is the volume of ν moles of the uid. Consider
an arbitrary point M on the line AB at whi h the number of moles of gas Here one makes use of onservation of the net mass of the uid: ml + mg .
Substitution of Eqs. (1.22) and (1.23) into Eq. (1.21) gives: Here the kineti energy of the ow is not taken into a ount sin e the ow
velo ity is assumed to be negligible ompared to the speed of sound c0 ,
Vl Vg otherwise the ee t ould not be observed. The ensuing error, e.g. of the
VM = (ml )M + (mg )M ,
ml + mg ml + mg temperature in rement, is of the order (u2 /c20 )T1 where u is the velo ity of
the ow. This estimate follows from Bernoulli's equation whi h repla es the
when e
(ml )M Vg − VM MB above equation when the kineti energy of the ow is not negle ted.
(mg )M
=
VM − Vg
=
AM
. Enthalpy H is a thermodynami fun tion similar to internal energy whi h
is dened as
Therefore the point M divides the line AB in two segments, AM and H = U + P V. (1.25)
M B whi h are inversely proportional to the masses of liquid and gas in
The above derivation shows that it is enthalpy that remains onstant during
a ordan e with Eq. (1.20).
the Joule-Thomson pro ess:
Let us al ulate the internal energy of van der Waals uid. Taking P
H1 = H2 . (1.26)
from Eq. (1.18) and substituting into Eq. (1.9), dierentiating, and then
integrating one obtains: Equation (1.26) allows one to al ulate parameters of a gas for ed through
a porous plug or another hydrauli resistan e. Quantitatively the Joule-
∂U a a Thomson ee t is spe ied by the ratio of the temperature dieren e ∆T =
= 2, U = − + f (T ).
∂V T V V = T1 − T2 to the pressure dieren e ∆P = P1 − P2 , where the indi es 1 and
2 orrespond to the quantities before and after the plug.
By denition (∂U/∂T )V = Cv (T ), therefore Consider the dierential Joule-Thomson ee t, i.e. the ase when the
Z respe tive pressure and temperature hanges are small:
a
U = − + Cv (T ) dT.
V ∆P ≪ P1 , ∆T ≪ T1 .
It is often assumed that Cv is temperature independent, then the internal In this ase the Joule-Thomson oe ient µJ−T , whi h is equal to the ratio
energy be omes of the temperature in rement to the pressure dieren e, is approximately
a
U = Cv T − . (1.24) equal to the derivative of pressure with respe t to temperature taken at
V onstant enthalpy:
∆T ∂T
The Joule-Thomson ee t. The Joule-Thomson ee t des ribes the µJ−T = ≈ . (1.27)
temperature hange of a gas whi h is for ed through a heat insulated porous ∆P ∂P H
plug (throttling pro ess) with a large hydrauli resistan e. The temperature Assuming that enthalpy is a fun tion of temperature and pressure and taking
of ideal gas, whi h mole ules neither attra t nor repel ea h other, is not into a ount that it is onserved during the pro ess one obtains:
hanged.
∂H ∂H
During stationary ow of the gas through the plug, the work done on dH = ∆T + ∆P = 0. (1.28)
the gas to for e it through the plug in reases the internal energy of the gas. ∂T P ∂P T
The energy dissipated in the plug due to fri tion remains in the ow. As a This gives the Joule-thomson oe ient:
result, the gas enthalpy remains onstant.
Consider the ow pro ess in detail. The work done to move one mole of ∂T (∂H/∂P )T
µJ−T = =− . (1.29)
gas to the plug at onstant pressure is P1 V1 . On the other side of the plug ∂P H (∂H/∂T )P
the work is performed against the ow and equals (−P2 V2 ); here V1 and V2 To evaluate the derivatives we use the rst and the se ond laws of
are molar volumes. The net work hanges the internal energy of gas, U2 −U1 , thermodynami s. The rst law (1.4) written in terms of enthalpy H is
as
P1 V1 − P2 V2 = U2 − U1 or P1 V1 + U1 = P2 V2 + U2 . δQ = dH − V dP.
Let H = H(T, P ), therefore The temperature Ti at whi h the dierential ee t vanishes is alled the
inversion point:
∂H ∂H 2a
δQ = dT + − V dP. (1.30) Ti = . (1.36)
∂T P ∂P T Rb
A ording to Eq. (1.35) during the dierential Joule-Thomson pro ess in
Using Eq. (1.5) we nd the following expression for the heat apa ity at whi h the pressure de reases as a result of the throttling the temperature of
onstant pressure Cp , i.e. at dP = 0: a raried gas in reases if the initial temperature is above Ti and de reases
if it is below Ti .
∂H
Cp = . (1.31) Inversion point of van der Waals uid in general ase. A general
∂T P expression for the temperature of inversion point depends not only on the
initial temperature T1 and volume V1 but on the nal volume V2 as well.
For arbon dioxide the experimental value is Cp = 41 J/(mol·K).
Let us substitute the internal energy of van der Waals uid (1.24) and
To obtain the derivative (∂H/∂P )T we follow the same steps as in
the pressure (1.18) into the enthalpy onservation formula (1.26):
the derivation of internal energy (1.9). Substitution of entropy (1.7) into
Eq. (1.30) gives: a

RT1 a

a

RT2 a

Cv T1 − + − V1 = Cv T2 − + − V2 . (1.37)
V1 V1 − b V12 V2 V2 − b V22
1 ∂H 1 ∂H
dS = dT + − V dP. (1.32)
T ∂T P T ∂P T At the inversion point T1 = T2 = Ti . Substitution into Eq. (1.37) gives:
A ording to the se ond law of thermodynami s dS is exa t dierential, so

V1 V2 1 1
RTi − = 2a − .
V1 − b V2 − b V1 V2
∂ 1 ∂H ∂ 1 ∂H
= −V .
∂P T ∂T P ∂T T ∂P T After simpli ation this equation gives the expression for the inversion
temperature whi h is valid at any nite hange in pressure and/or volume:
This gives the desired derivative after dierentiation and simpli ation:
2a (V1 − b)(V2 − b)
(1.38)

∂H ∂V Ti = .
=V −T . (1.33) Rb V1 V2
∂P T ∂T P
For the dierential Joule-Thomson ee t at V1 ∼ V2 and any relation
Substituting Eqs. (1.31) and (1.33) into Eq. (1.29) one nds: between V1 and b this gives:
2
∂T T (∂V /∂T )P − V 2a V1 − b
µJ−T = = . (1.34) Ti = . (1.39)
∂P H Cp Rb V1
For ideal gas P V = RT and the Joule-Thomson oe ient vanishes. For the dierential ee t and raried gas, i.e. for V1 ≫ b, one obtains Ti =
The Joule-thomson ee t for van der Waals uid. Let us nd the Joule- 2a
= Rb . This result oin ides with Eq. (1.36).
Thomson oe ient for van der Waals uid using equation of state (1.18). For the so- alled integral ee t and V2 ≫ b one has
Taking the derivative in a ordan e with Eq. (1.18) one an power expand
the obtained result (Eq. (1.34)) and leave only the terms linear in the 2a V1 − b
Ti∞ = . (1.40)
parameters a and b. This gives: Rb V1
2a
−b Heat apa ity of solids.. Mole ules and atoms of solids are bound together
µJ−T = RT
. (1.35) by intera tion for es and are able only to vibrate near equilibrium positions
Cp
16 THERMODYNAMIC PROCESSES 2.1.1 17
at the latti e sites. The vibrational energy is the internal energy of a solid, 2.1.1. Measurement of spe i heat of air at
it determines the body temperature. Thus a solid an be onsidered as a onstant pressure
set of vibrating parti les, the os illators. The average kineti energy of a
harmoni os illator equals the average potential energy. (Potential energy Purpose of the lab: 1) to measure the in rease in temperature of the
is proportional to the squared displa ement whi h time dependen e is a air owing through a heater; 2) to al ulate the heat apa ity of air at
harmoni fun tion and the kineti energy is proportional to the squared time onstant pressure using the results.
derivative of the displa ement; the average of a harmoni fun tion squared Tools and instruments: a heat insulated glass tube; an ele tri heater;
is phase independent.) Therefore one degree of freedom of the os illator has the sour e of dire t urrent Á5-47; a thermo ouple; an ammeter; a
twi e as mu h energy as that of a free parti le, i.e. kT . Sin e every atom of a voltmeter; the universal digital voltmeter Â7-23; a gas meter; and a
solid is able to vibrate in three spatial dire tions, i.e. it has three degrees of stopwat h.
freedom, the total energy per atom is 3kT and the energy per mole is 3RT .
Thus the molar heat apa ity of a solid is C = 3R. A ording to the above Usually heat apa ity is measured by means of a alorimeter: a ontainer
argument it is the heat apa ity at onstant volume. whi h provides heat insulation of the studied obje t from the environment.
So, a ording to lassi al theory molar heat apa ities of all solids are One measures the heat Q transferred to the obje t and the orresponding
independent of temperature and equal to 3R. This theoreti al predi tion hange of its temperature ∆T . The heat apa ity is dened as the ratio of
agrees well with the empiri ally established Dulong-Petit law whi h states Q to ∆T :
that molar heat apa ities of all solids are approximately equal to 6 al/(mol·deg). Q
C= .
The theoreti al value C = 3R = 24.94 J/(mol· ◦ C)= 5.96 al/(mol· ◦ C). ∆T
(1 al= 4.1868 J). The a ura y of the measurement is mostly determined by the alorimeter
At room temperature the Dulong-Petit law holds for many elements quality. The heat supplied to the obje t under study must signi antly
in luding metals fairly well. At low temperatures the heat apa ity de reases ex eed the heat transferred to the alorimeter and the heat es aped to the
and tends to zero at zero temperature. This phenomenon is due to quantum environment. It is very di ult to meet this requirement in the measurement
ee ts; it was explained by Debye. The Debye theory has a single parameter, of heat apa ity of air be ause the mass of the air ontained in a alorimeter
the so- alled Debye temperature θ; above θ the heat apa ity of a solid and therefore the heat transferred to the air are very small. To in rease
in reases with temperature only by 5%. For aluminum θ = 394 Ê and for the amount of air in the laboratory installation the air is sent through
iron θ = 420 Ê. For both metals the Debye temperature ex eeds the room a alorimeter with a heater inside. The measured quantities in lude the
temperature, so for these metals the theoreti al values of heat apa ity at supplied heat, the mass of the air passed through the alorimeter, and the
T = 300 Ê are approximately 8% less than the maximum value. in rease in the air temperature.
Laboratory setup. The experimental setup is shown in Fig.1. The valve Ê
serves to ontrol the amount of air entering the installation. The volume of
air passed through the alorimeter is measured by means of the gas meter
Ñ.
The alorimeter is a glass tube pla ed within an eva uated ontainer. The
pressure in the ontainer does not ex eed 10−5 torr, the heat ondu tivity
at this pressure is negligible. The ontainer walls fa ing the tube are silver
oated, whi h redu es heat losses due to radiation.
The heater is made of a wire mesh onne ted to the sour e of dire t
urrent Á5-47. The air owing through the heater ools it. There is a
spe ial swit h to prevent the heater from being burned-out if the air ow
is obstru ted or its velo ity is not su ient. The ammeter and voltmeter
are in luded into the ir uit to measure the power supplied to the heater.
Here P1 , V1 and P2 , V2 are the pressure and the molar volume of in oming
DC Power and outgoing air, respe tively.
A
Unit Б5-47 The internal energy of air hanges by the amount ∆U = U2 − U1 .
Let us use the rst law of thermodynami s to determine the heat Q
V
transferred to the air: (1.1):
Q = U2 − U1 + P2 V2 − P1 V1 = H2 − H1 ,
Vacuum
where H = U + P V is enthalpy. Thus, the transferred heat in reases the air
K Heater enthalpy (noti e that the hange in kineti energy of air an be negle ted
Heated air
GM Air sin e the velo ity of air ow in this experiment is small ompared to that of
Thermocouple Thermocouple the sound).
(1st junction) (2nd junction) For ideal gas H = Cp T , so
epla ements
Digital Vacuum
Q = Cp (T2 − T1 ).
voltmeter
B7-23
Therefore the heat apa ity in this experiment is measured at onstant
Ñ pressure; this is be ause the pro ess is stationary.
The spe i heat apa ity is al ulated by means of the formula:
Fig. 1. Experimental setup
Q IV − N
cp = = , (1)
The temperature gradient is measured by means of the opper- onstantan m∆T m∆T
thermo ouple. One jun tion is pla ed in the air ow entering the alorimeter where IV is the power onsumed by the heater, N is the power of thermal
and the other one is in the outgoing ow. The thermo ouple emf is losses, m is the mass rate of the air going through the alorimeter, and ∆T
proportional to the temperature dieren e, it is measured by the universal is the temperature dieren e measured by the thermo ouple.
digital voltmeter Â7-23. The thermo ouple emf equals 4.23 mV at the
temperature dieren e of 100 ◦ C (the old jun tion is at room temperature). LABORATORY ASSIGNMENT
At the beginning of the experiment, right after the heater is swit hed 1. Prepare the air meter: make sure that it is lled with water and level it.
on, the power is onsumed mostly to heat up the alorimeter. When the Open the valve K. Inspe t the tube jun tions and make sure there are no
temperature distribution be omes stationary, the power is shared between air leaks. The working range of the meter is 0.030.5 l/s. If the air ow is
heating the air and thermal losses in the alorimeter walls. below the minimum the spe ial swit h turn the heater power o.
Noti e that the thermal losses depend only on the temperature distribution
2. Turn on the swit hes ¾power¿ and ¾blo k¿ of the voltmeter. Verify that the
along the walls and therefore on the temperature dieren e measured by
thermo ouple emf is zero when the air is owing through the alorimeter
the thermo ouple. The losses are independent of the air ow and the power
and the heater is turned o .
onsumed by the heater. This observation allows one to evaluate the thermal
3. Set a moderate voltage (up to 10 V) on the power unit Á5-47 and turn it
losses experimentally and take them into a ount.
on.
Let us evaluate the work performed by the air owing through the
alorimeter. The work done to sent one mole of air into the tube is A1 = 4. Measure the rate of air ow, the heater power, and the temperature
= P1 V1 . At the end of the tube the external pressure is against the ow and dieren e at various modes of operation. The measurements should onsist
the work is negative: A2 = −P2 V2 . The net work is A1 + A2 = P1 V1 − P2 V2 , of two or three runs. The voltage of the power unit and the rate of air
the work done by the air has the opposite sign: ow should be varied so that the readings of the thermo ouple voltmeter
remained the same in every run: this means the same heat losses. The
A = P2 V2 − P1 V1 . temperature dieren e should be hosen within the range of 520 ◦ C. Every
run must onsist of 56 measurements at various ow rates and therefore at
various powers onsumed by the heater. Ê
Make sure that the ow has be ome stationary before re ording the
readings. This an be ontrolled by observing the readings of the thermo ouple
voltmeter. The dispersion of its readings should not ex eed 0.2 ◦ C in every Ì
run.
5. For every run plot the heater power IV on the abs issa and m∆T on the
ordinate. The mass m of the air owing through the alorimeter per se ond
should be determined by the ow rate measured by the gas meter. The PSfrag repla ements
air density is determined a ording to the readings of the barometer and
thermometer in the laboratory room. Ê1
À
The slope of the straight line drawn through the points determines the
heat apa ity of air at onstant pressure. The inter epts with the abs issa
are equal to heat losses N . Fig. 1. Experimental setup for measuring Cp /Cv ratio by
6. Estimate the heat losses under two assumptions: the losses are mostly due method of adiabati expansion
to heat ondu tivity and the losses are mostly due to radiation. Whi h of
the assumptions is better supported by the data? 2.1.2. Measurement of Cp /Cv ratio of gas by the
7. Find the main sour es of experimental errors and estimate them. method of adiabati expansion.
Literature
Purpose of the lab: to determine Cp /Cv ratio for air and arbon
1. Áåëîíó÷êèí Â.Å., Çàèêèí Ä.À., Öèïåíþê Þ.Ì. Îñíîâû èçèêè. Ò. 2. Êâàí
dioxide by measuring the pressure in a glass ontainer. The measurement
òîâàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 2, 2.1,
is performed twi e: before adiabati expansion and after iso hori warming
2.2.
to the ambient temperature.
2. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976.
ë. IX, 2427.
Tools and instruments: a glass ontainer; a liquid olumn manometer;
3. Ëàíäàó Ë.Ä., Àõèåçåð À.È., Ëèøèö Å.Ì. Êóðñ îáùåé èçèêè. Ì.: Íàóêà,
a rubber dou he; and a gasometer with arbon dioxide.
1965. ë. VII, 57.
4. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001.
Ñ. 98107. Laboratory setup. The experimental setup onsists of a glass ontainer A
5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1. (about 20 l in volume) with a tap K and an U-shaped tube water manometer
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 158170. to measure the ex essive gas pressure in the ontainer. The setup is shown
in Fig. 1.
The pressure ex ess is reated either with the rubber dou he (for air
measurements) onne ted with the ontainer by the tubing inlet and a tap
Ê1 or, in the ase of CO2 measurements, with the pressure regulator of the
gasometer.
At the beginning of the experiment the ontainer A is lled with a
gas at room temperature T1 and a pressure P1 whi h slightly ex eeds
the atmospheri pressure P0 . Then one opens the tap K; the pressure
and temperature in the ontainer drop. This pro ess is assumed to be
adiabati be ause in gases the pressure omes to equilibrium mu h faster
than the temperature. Thermal equilibrium is rea hed via the pro ess of
"heat diusion namely, the diusion of intensity of haoti motion. Therefore Eliminating the ratio T1 /T2 from Eq. (3) by using Eq. (4) we obtain
γ γ−1
∆tP ≪ ∆tT , (1) P3 P1
= .
P2 P2
where ∆tP and ∆tT stand for the time of pressure and temperature
equalization, respe tively. Taking into a ount that P2 = P0 we obtain for γ :
The validity of the ondition (1) depends on the setup design, in
ln(P1 /P0 )
parti ular, on the size of the outlet hole in the tap K whi h should be γ= . (5)
ln(P1 /P3 )
su iently large. Below we estimate the values of ∆tP and ∆tT and dis uss
their inuen e on the a ura y of the experiment. If the tap K is opened In our ase the dieren es between P1 , P3 and the atmospheri pressure
during the time interval ∆t whi h satises the ondition are small and an be measured by the U-shaped liquid manometer. Let us
use the notations:
∆tP ≪ ∆t ≪ ∆tT , (2)
P1 = P0 + ρg h1 , P3 = P0 + ρg h2 .
the heat ex hange through the ontainer walls an be negle ted and the
prosess an be onsidered adiabati . Expanding logarithms in power series and dropping the terms of the se ond
Let us rewrite the adiabati equation (1.15) in variables P , T using the order we nally obtain
ideal gas law. The gas state orresponding to the in reased pressure and the
ln(1 + ρg h1 /P0 ) h1
temperature equal to the room temperature is denoted by subs ript "1". The γ= ≈ . (6)
gas state immediately after opening the tap and the pressure equalization ln(1 + ρg h1 /P0 ) − ln(1 + ρg h2 /P0 ) h1 − h2
is denoted by subs ript "2". We obtain One an arry out the exa t al ulations based on Eq. (5) and thus
γ−1 γ estimate the error of the approximation (6).
P1 T1 To determine γ by means of Eq. (6) one measures the values of the
= . (3)
P2 T2 ex essive pressures before the adiabati expansion and after the iso hori
warming. Both pressures should be measured at the state of thermodynami
The pressure P2 after the adiabati expansion is equal to the atmospheri
equilibrium. To this end the tap K should be losed right after the pressure
pressure P0 , while the temperature T2 drops below the room temperature
in the ontainer equalizes with the atmospheri pressure but before the heat
T1 due to the work performed by the expanding gas at the expense of its
ex hange starts, i.e. it is important to meet the ondition (2).
internal energy1 .
When the ontainer is isolated from the environment by the tap K, a The time of gas outow. In our experiment the gas ows into the open air
slow iso hori warming of the gas takes pla e, the rate is determined by through a wide and short tube. This allows one to negle t the gas vis osity
the thermal ondu tivity of the ontainer walls. The gas pressure in reases when estimating the time ∆tP of pressure equalization.
together with the temperature. The system rea hes thermal equilibrium When the tap K is opened a depression wave propagates in the gas
during the time ∼ ∆tT , the temperature T3 be omes equal to the room at the speed of sound c, the wave rea hes the ontainer bottom during
temperature T1 . the time of L/c (where L is the ontainer height). By this time the bulk
The iso hori pro ess is des ribed by Charles' law: of gas is set in motion; the runout pro ess be omes quasistationary after
several os illations. Sin e the gas pressure is lose to the atmospheri one
P2
=
P3
=
P3
. (4) and density variations an be negle ted one an use Bernoulli's equation for
T2 T3 T1 in ompressible uid to estimate the outow speed v :
1 It is more onvenient to use P , T variables rather than the P , V ones be ause s
the hange in the amount of gas during the expansion does not ae t its pressure and 2(P − P0 )
v= .
temperature but should taken into a ount if volume is used. ρ0
The mass of gas leaking through the area Sr of the tap ori e during a this time is small ompared to the ontainer size, so the pro ess may
time interval dt is given by ρ0 Sr v dt, where the density ρ0 is taken at the be onsidered as one-dimensional. The pro ess of temperature evolution
atmospheri pressure as dis ussed above. in spa e and time is des ribed by the heat equation (partial dierential
A pressure de rease dP in the ontainer volume V0 due to adiabati equation) whi h solution is ompli ated even in the one-dimensional ase.
expansion during the same time is related to the mass de rement as Here we onne ourselves to an estimate.
All physi al properties of the medium parti ipating in the heat transfer
V0 are represented in the heat equation by a single parameter alled thermal
dm = V0 dρ = dP.
c2 diusivity χ = ρcκp , where κ is the thermal ondu tivity, cp is the spe i
Here we use the denition of the adiabati speed of sound heat apa ity at onstant pressure, and ρ is the medium density. In SI, the
unit of thermal diusivity χ is m2 /s.
∂P In the pro ess of heat propagation from a at wall the initial temperature
c2 = .
∂ρ S distribution does not ontain parameters with the dimension of length,
2
so the solution depends on a single dimensionless parameter xχt , where
Equating the masses we obtain the dierential equation: x is oordinate and t is time (su h an approa h is alled the self-similar
√ solution). A value of the parameter orresponds to a denite temperature.
dP 2ρ0 Sr c2
√ =− dt. The distan e from the wall to the point with a given temperature in reases
P − P0 V0 2
as the square root of time. In the exa t solution the parameter value xχt = 1,
√
Integrating the equation we determine the desired time of gas outow: or equivalently, x = χt, orresponds approximately to the average of the
s wall temperature and the original gas temperature. This value of x an be
V0 2(P − P0 ) used as the approximate thi kness of the gas layer heated by the ontainer
tP = . (7) wall during the time of the "adiabati "outow.
Sr c γP0
In a ordan e with the estimated value of tP let us assume the time
Let us make a quantitative estimate using the parameters of our of onta t between the ontainer and the atmosphere to be t = 0.5 s. For
experimental setup: the ontainer diameter is 25 m, the diameter of the the ambient air we have cp = 0.99 J/(g·K), ρ = 1.29 kg/m3 , and κ =
ori e is 1 m, L = 50 m, c = 340 m/s, γ = 1.4, and P − P0 = 10 m H2 O. = 2.50 · 10−2 W/(m·K). Thus we obtain χ = 0.19 m2 /s and for t = 0.5 s
This results in tP = 0.1 s. the depth of heating equals x = 0.3 m.
During the al ulated time an a ousti wave traverses the ontainer from For the ontainer radius R = 12.5 m the amount of gas that does
the top to the bottom 34 times. This is enough to justify the approximation not undergo adiabati ooling is 2πRx πR2 = 0.05 or 5% of the total mass
of quasistationary gas ow and the usage of Bernoulli's equation. of gas. Therefore the pressure P3 and the measured value of h2 are
It is worth noti ing that after the pressure is stabilized the resonant approximately 1.05 times less than the values al ulated above. This leads
a ousti os illations an take pla e in the ontainer be ause of the ow to underestimation of γ by a fa tor of h1h−h
2
2
·0.05 (a ording to Eq. (6)). For
inertia. Therefore, if the tap K is opened for a short time ∆t < 1 s, the results example for h1 = 20 m and h2 = 10 m the relative error of γ is also 5%.
of individual measurements will dier signi antly (the random s atter is This is omparable with the dieren e between the Cp /Cv ratio of diatomi
also due to un ertainty of ∆t). During the time ∆t > 1 s the pressure (1.40) and polyatomi (1.33) gases predi ted by the lassi theory. However
os illations are suppressed by vis ous damping but the heat ex hange we have not yet taken into a ount the ooling of the glass walls, whi h
in reases, whi h results in a de rease of pressure P3 and underestimation might redu e the estimated error.
of γ .
Cooling of the walls. The depth of ooling of the ontainer walls during
Heat ex hange through the ontainer walls. Let us estimate the the gas outow an be estimated in the same way as above.
heat transfer between the gas and the ontainer walls during the pressure The relevant glass parameters are: the heat apa ity c = 1.0 kJ/(kg·K),
equalization time of about 0.5 s. The depth of thermal diusion during the spe i density ρ = 2.5 · 103 kg/m3 , and the thermal ondu tivity κ =
= 1.0 W/(m·K). Therefore we obtain χ = 0.4 · 10−2 m2 /s and the ooling 4. Estimate the error of the result.
depth of 0.045 m only.
From this estimate one an see that the thi kness of glass whi h Questions
undergoes the ooling is about seven times smaller than the orresponding 1. Does γ depend on temperature in the hosen temperature interval?
depth of the gas layer. If we take into a ount that the volumetri heat 2. What are the values of Cp , Cv , and γ for an ideal gase a ording to the
apa ity of glass is 3 orders of magnitude greater than that of air, a variation equipartition theorem?
in the temperature of glass walls is approximately one hundred times smaller 3. Why does the gas temperature in rease when the ontainer is being lled?
than that for a gas. Therefore the glass ooling does not noti eably inuen e 4. Evaluate the time of gas outow using the Poiseuille equation.
the nal result.
Literature
To summarize, the heat transfer during the time of the gas outow
1. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. I. Ìåõàíèêà. Ì.: Íàóêà, 1989. 94;
signi antly ae ts the a ura y of the measurement leading to underestimated
Ò. II. Òåðìîäèíàìèêà è ìîëåêóëÿðíàÿ èçèêà. Ì.: Íàóêà, 1990. 22, 56.
values of γ . Hen e it is re ommended to perform several measurements with
various durations of the outow and then interpolate and extrapolate the
òîâàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 2, 2.1,
results. 2.2.
LABORATORY ASSIGNMENT ë. II, 2427.
1. Before the beginning of the experiment make sure that the valves and joints 4. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001.
of the tubes are airtight: ll the ontainer with air or arbon dioxide until Ñ. 98112.
the pressure ex eeds the atmospheri one by 1025 m of water and lose the 5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1.
tap Ê1 . The pressure rise is followed by the temperature in rease. Due to Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 158174.
thermal ondu tivity of the ontainer walls the gas temperature gradually
de reases along with the pressure (iso hori ooling). Using the U-shaped
water manometer, measure the dependen e of pressure h on time t and
2.1.3. Determination of Cp /Cv ratio of gas by
draw a plot h = f (t). If the setup is airtight enough the pressure stabilizes
during the time of thermalization ∆tT . If this is not the ase a leakage measuring the speed of sound in it.
should be found and xed. Determine the thermalization time ∆tT from the
Purpose of the lab: 1) to measure the frequen y of os illations and the
plot. A stable ex essive air pressure h1 in the ontainer should be arefully
wavelength of gas at a ousti resonan e in a tube; 2) to determine the
measured. adiabati index by applying the ideal gas law.
2. Open the tap K for a short time and lose it again. Wait until the water level
in the manometer omes to rest. This time is approximately equal to the Tools and instruments: an audio-frequen y generator AG; an ele troni
thermalization time ∆tT . Write down the dieren e h2 between the water os illos ope EO; a mi rophone; a speaker; a teles opi tube; a thermally
levels. It is re ommended to perform 58 measurements. Ea h measurement insulated tube heated with water from the thermostat; a ontainer with
in ludes: lling the ontainer, waiting till h1 levels o, and opening the tap K ompressed arbon dioxide; and a gasometer.
for about ∆t = 0.5 s afterwards. This time orresponds to a qui k turn of the
tap by 180◦ . Next 58 measurements should be taken for the outow time The speed of a ousti wave in a gas depends on its adiabati index γ .
of 0.51.0 s, and the nal 58 measurements for the interval of 1.55 s. Ea h Measurement of speed of sound is one of the most a urate ways to determine
time re ord h1 and h2 after the pressure equalizes. Using the data obtained γ.
and Eq. (6) al ulate the values of γ and plot the dependen e γ(∆t). Speed of sound in a gas is dened by Eq. (1.17):
3. The nal result should be determined by extrapolating the dependen e of γ s
on ∆t to a value of ∆t = 0.10.2 s, at whi h the pressure is approximately RT
c= γ ,
atmospheri and the inuen e of thermal ondu tivity on γ an be negle ted. µ
where R is the gas onstant, T is the temperature, and µ is the molar mass wavelength of sound λ should gradually be tuned. The su essive resonan es
of the gas. Solving the equation for γ we nd: are related as
µ 2 λ1 λ2 λk+1
γ= c . (1) L= n= (n + 1) = . . . = (n + k). (4)
RT 2 2 2
Hen e to determine the adiabati index, one needs to measure the gas From Eqs. (3) and (4) one obtains
temperature and the speed of sound in it (the molar mass is supposed to be c c c c c
known). f1 = = n, f2 = = (n + 1) = f1 + , ...,
λ1 2L λ2 2L 2L
An a ousti wave propagating along a tube is ree ted by the tube ends.
The resulted pattern of sound vibrations is the superposition of the ree ted c c c
fk+1 = = (n + k) = f1 + k. (5)
waves and, in general ase, it is ompli ated. The pattern is simplied if the λk+1 2L 2L
tube length L is equal to an integer number of half-waves, Thus the speed of sound divided by 2L is determined by the slope of the
λ urve representing the dependen e of frequen y on the resonan e #.
L=n , (2)
2 Laboratory setup. Two setups (see Figs. 1 and 2) are designed to measure
the speed of sound using both methods des ribed above. In ea h setup the
where λ is the wavelength and n is the integer. If the ondition (2) is fullled, a ousti waves in the tube are ex ited by the speaker T and re eived by the
the phases of an in ident wave and the wave ree ted from both ends of the mi rophone M. The speaker membrane vibrates due to alternating urrent of
tube oin ide. As a result, they amplify ea h other. The wave amplitude a ousti frequen y; the audio-frequen y generator AG is used as the sour e.
sharply in reases and resonan e o urs. A signal re eived by the mi rophone is visualized on the os illos ope EO.
At the tube ends there is no displa ement of air parti les (a node). Other The mi rophone and the speaker are onne ted to the main setup by thin
nodes (if any) along the tube are separated by λ/2. Anti-nodes, in whi h the rubber pipes. Su h a onne tion ensures proper ex itation and dete tion
amplitude is at maximum, are entered between the nodes. of a ousti vibrations and at the same time it only slightly perturbs the
The speed of sound c is related to its frequen y f and the wavelength λ vibrations. So, both ends of the tube may be onsidered as sealed and the
as inuen e of the inlet pipes an be negle ted.
c = λf. (3) The rst setup (Fig. 1) in ludes the teles opi tube with a millimeter
s ale. Through a tubing inlet (not shown in the gure) the tube is lled
A resonan e an be obtained by two ways: either with air or with arbon dioxide from the gasometer. This setup is
1. The tube length L an be varied at a xed frequen y f of the a ousti used for measurement of γ of air and CO2 at room temperature. The se ond
generator, i.e. at a onstant wavelength of sound λ. A teles opi tube is setup (Fig. 2) ontains a thermally insulated tube of xed length. A gas in
used for this purpose. The length of the tube is gradually in reased and a this tube is heated by water from the thermostat, so the gas temperature is
sequen e of resonan es is dete ted. The onset of a resonan e an be easily onsidered equal to that of the thermostat. The setup is used for studying
observed on the os illos ope s reen as a sharp rise of the amplitude of a dependen e of the speed of sound on temperature.
a ousti os illations. For su essive resonan es
λ λ λ λ LABORATORY ASSIGNMENT
Ln = n , Ln+1 = (n + 1) , . . . , Ln+k = n +k . 1. Plug in the ele troni os illos ope EO and the audio-frequen y generator
2 2 2 2
AG, press the power swit hes, and let the devi es warm up for 57 minutes.
In other words, λ/2 is equal to the slope of the linear dependen e of tube Then obtain the signal line on the s reen by adjusting the ontrols of the
length L on the resonan e # k . The speed of sound is given by Eq. (3). os illos ope.
2. One an also vary the frequen y of a ousti os illations at a onstant Set the zero frequen y on the a ousti generator (only for generator
length of the tube. In this ase, the generator frequen y f and therefore the Ç-18). To do this, set the limbs "Frequen y"and "Dephasing"at zero,
then make the voltmeter pointer stop at zero by turning the knob "Zero
adjustment". Che k the zero setting during the experiment.
2. Adjust the amplitude of the AG output to mat h the range of the EO s reen
at a resonan e. Attain a stable waveform display. Make sure the os illations
have undistorted sinusoidal shape. If the observed waveform is distorted,
de rease the amplitude of the output generator signal until the distortion is
Ç
gone.
ÝÎ
3. The rst setup (Fig. 1).
a) Using an approximate value of the speed of sound (300 m/s) al ulate
the frequen y range in whi h 25 resonan es an be observed by extending
PSfrag repla ements the tube.
Ò Ì
b) To purge the tube from a remaining arbon dioxide blow air into
it using either the inter epting valve or the pushbutton. Dete t all the
resonan es available for observation by gradually hanging the tube length.
Repeat the measurements at various frequen ies (46 values overall). For
Fig. 1. Setup for measuring speed of sound ea h resonan e re ord the orresponding lengthening of the tube. Carry out
with the aid of teles opi tube the measurements by in reasing the tube length and then by de reasing it.
) Plot a resonan e # k on the abs issa and the orresponding tube
lengthening Ln+k − Ln on the ordinate. Fit a straight line to the points
obtained at a xed frequen y. The slope of the line gives the half-wavelength.
Estimate the error of λ/2 using the plot. Cal ulate the speed of sound
and estimate the error. (The error of the frequen y s ale does not ex eed
a half of the smallest s ale graduation.) Compare the speeds measured at
Ç dierent frequen ies. Do they agree? Find the best value of the speed of
ÝÎ sound by using the whole set of the results.
d) Measure the speed of sound in arbon dioxide. Before the experiment
blow arbon dioxide into the tube by slowly pulling out and qui kly pushing
to thermostat
ba k the mobile part of the tube. Repeat the pro edure several times. The
PSfrag repla ements gas is at room temperature. The position of a resonan e maximum should
Ò Ì
be measured with open CO2 valve by slowly moving the mobile part of the
tube in both dire tions.
After ompleting this part of the experiment insert the moving part in
the tube to the end and arry out the measurements of the resonan e peaks
at the xed length; rst, by in reasing the frequen y and then by de reasing
from thermostat it. Compare the results with those obtained at various tube lengths.
Fig. 2. Setup for measuring speed of sound at various temperatures 4. The se ond setup (Fig. 2).
a) Measure the speed of sound in the tube of xed length. Gradually
in reasing the output frequen y re ord the su essive resonant frequen ies
dete ted by a sharp ampli ation of the signal on the os illos ope s reen.
As ertain reprodu ibility of the results by de reasing the frequen y.
b) Plot the dieren e between the k -th and the rst resonan e fk+1 − f1 orresponding temperature in rement ∆T of the obje t. The heat apa ity
as a fun tion of k . Fit a straight line to the points. The slope of the line is determined as
equals the value of c/2L (see Eq. (8)). Cal ulate the speed of sound and ∆Q
C= . (1)
estimate the error. ∆T
) Turn on the thermostat. Repeat the measurements of Se toins a) The temperature of the obje t an be reliably measured by a thermometer
and b) at three temperatures between the room temperature and 80 ◦ C. (in this experiment it is RTD) but the measurement of the heat transfer is
Cal ulate the speed of sound at ea h temperature. not so easy. The problem is that the energy P ∆t produ ed by the heater
5. Cal ulate the value of γ = Cp /Cv using Eq. (3). Estimate the error. tends to dissipate through the alorimeter walls, only part of the energy
is transferred to the obje t. So, the amount of heat ∆Q transferred to the
Questions alorimeter is
1. Derive the equations (1.16) and (1.17). ∆Q = P ∆t − λ(T − Tê )∆t, (2)
2. Does the value of γ depend on temperature in the onsidered temperature range? where P is the power dissipated in the heater, λ is the heat transfer
3. Is there su h a dependen e in the range from very small temperatures to 1000 ◦ C? oe ient of the alorimeter walls, T is the obje t temperature, Tr is the
ambient (room) temperature, and ∆t is the time of heating.
Literature
Combining Eqs. (1) and (2) one gets:
1. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. I. Ìåõàíèêà. Ì.: Íàóêà, 1989. 85;
Ò. II. Òåðìîäèíàìèêà è ìîëåêóëÿðíàÿ èçèêà. Ì.: Íàóêà, 1990. 23. P − λ(T − Tr )
C= . (3)
∆T /∆t
òîâàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 2, 2.2.
3. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976. Equation (3) is the main equation, it determines the net heat apa ity of
ë. II. 2427. the obje t and the alorimeter. The heat apa ity of the alorimeter should
4. Õàéêèí Ñ.Ý. Ôèçè÷åñêèå îñíîâû ìåõàíèêè. Ì.: Íàóêà, 1971. ë. XVI, 134. be measured separately and then subtra ted from the result.
ë. XIX. 154. As the temperature of the obje t grows the loss of heat through the
5. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001. alorimeter walls grows as well. Equation (2) shows that if the power
Ñ. 98111. dissipated in the heater is onstant the heat transferred to the obje t
6. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1. de reases when the temperature goes up and therefore the rate of the obje t
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 158173. temperature growth drops.
It seems that the error related to the heat losses an be made small if one
does not overheat the obje t and does the measurements at the temperatures
2.1.4. Measurement of spe i heat of solids lose to room temperature (T → Tr ). However this would result in a large
error of ∆T = T − Tr , so the error of the heat apa ity remains substantial.
Purpose of the lab: 1) to measure the temperature in rement versus the The following method is used to avoid this problem. The dependen e ∆T /∆t
amount of heat transferred to a solid obje t; 2) to determine the spe i is measured in a large temperature range. Then one plots the dependen e
heat apa ity by extrapolating the ratio ∆Q/∆T to zero heat losses.
∆T
= f (T ),
Tools and instruments: a alorimeter with a heater and a resistan e ∆t
thermometer (RTD); an ammeter; a voltmeter; a Wheatstone bridge; and whi h is extrapolated to room temperature T = Tr . Thus the rate of heating
a voltage sour e of 36 V. is determined at the room temperature, (∆T /∆t)T =Tê . Substituting the
result into Eq. (3) and dropping the term λ(T − Tr ), whi h vanishes at
In this experiment the heat apa ity of solids is measured a ording to T = Tr , one obtains:
the standard method. An obje t under study is pla ed in a alorimeter. P
One measures the amount of heat ∆Q transferred to the obje t and the C= . (4)
(∆T /∆t)Tr
Laboratory setup. The setup onsists of the

Í
Remote temperature PSfrag repla
alorimeter with a styrofoam insulation plaements
ed
Styrofoam detector (RTD) coil in the box made of thi k plywood. The internal
Сover Copper
wall of the alorimeter is made of a material
with high heat ondu tivity. A good thermal V
onta t between a studied obje t and the A
internal wall is due to their oni al shapes that =36 V Ê R
Bolt enables a tight t. The obje t an be pushed
Sample
out with the aid of a bolt in the alorimeter Fig. 2. Ele tri ir uit of heater
cavity bottom.
Heater coil The ele tri heater and the RTD are built in the alorimeter wall. The
Styrofoam ele tri ir uit is shown in Fig. 2. The potentiometer allows one to ontrol
the urrent in the heater ir uit. The heater power is determined by means of
Fig. 1. Calorimeter design the ammeter and the voltmeter. The RTD resistan e is measured by means
of the Wheatstone bridge.
The temperature is measured by the RTD whi h onsists of opper wire
wound around the internal heat ondu tive asing of the alorimeter (see LABORATORY ASSIGNMENT
Fig. 1).The ele tri al resistan e of the RTD varies with temperature as 1. Familiarize yourself with the alorimeter design. Set the Wheatstone bridge
-4833 ready to measurements, namely, plug the power ord to the so ket,
RT = R0 (1 + α∆T ), (5) he k the RTD onne tions to terminals Ò1 and Ò2 (Ò1 and Ò2 are onne ted
to terminals Ï1 and Ï2 , respe tively), press the buttons ¾power¿, , ÌÎ-4,
where RT is the thermometer resistan e at T ◦ C, R0 is the resistan e at and ⌢\ .
0 ◦ C, and α is the temperature oe ient. 2. Measure the RTD resistan e at room temperature Tr . To this end set the
Dierentiating Eq. (5) with respe t to time one obtains: ratio of the bridge legs to N = 1 on the bridge front panel and balan e the
bridge by pressing the knob H (the galvanometer is onne ted via a large
dR dT resistan e). This gives a oarse value of the RTD resistan e. To rene it
= R0 α . (6)
dt dt hoose the ratio of the legs N whi h orresponds to the maximum a ura y
(all ontrol knobs of the potentiometer are involved). Balan e the bridge
Let us express the resistan e R0 in terms of the RTD resistan e Rr measured
again by pressing the knob H (Coarse) and then the knob HH (Pre ise:
at the room temperature. A ording to Eq. (5)
the galvanometer is onne ted without the resistan e).
Rr 3. Close the swit h K for a short time and set the potentiometer resistan e
R0 = . (7) orresponding to the power of 1012 W. Turn the heater o. The setup is
1 + α∆Tr
now ready for measurements.
Substituting Eqs. (6) and (7) into Eq. (4), one obtains 4. Measure the dependen e of the RTD resistan e on time, RT = R(t), for the
empty alorimeter and at a onstant power of the heater. Before doing this
P Rα he k that the bridge is balan ed and if this is not the ase verify the initial
C= . (8)
dR
dt Tr (1 + α∆Tr ) resistan e of the RTD. Then lose the swit h K and simultaneously start
the stopwat h. Set the resistan e of the bridge leg a bit above (by ∼0.5%)
The temperature oe ient of opper is α = 4.28 · 10−3 Ê−1 , other the balan e (the galvanometer hand will deviate from the neutral position)
quantities are determined in the experiment. and observe the motion of the galvanometer hand. Re ord the stopwat h
readings at the moment when the balan e is a hieved, so that the RTD
resistan e be omes equal to that of the bridge leg. Then in rease the leg 2.1.5. Experimental study of thermal ee ts
resistan e and re ord the moment of balan e, et . Obtain 1015 points. aused by elasti deformations
5. Plot the points using the values of resistan e as ordinates. Draw a smooth
Purpose of the lab: 1) to study experimentally elasti deformation of
urve through the points.
rubber band in luding the ase of large elongation when the deformation
6. Using the plot of RT = R(t) determine the dependen e dR/dt = f (R). To be omes non-linear; 2) to measure band heating at large adiabati
do this divide the urve RT = R(t) into 1015 intervals and al ulate the stret hing and to determine its heat apa ity.
slope dR/dt for every interval. Plot the points (t, dR/dt) on a new graph.
Tools and instruments: a rubber band xed in an installation; a set of
Extrapolate the obtained urve to the point RT = Rr
weights; a thermo ouple; and a voltmeter Ô-116/1.
7. Substitute the obtained values of (dR/dt)R=Rr and Rr into Eq. (8) and
al ulate the heat apa ity C0 of empty alorimeter. Deformation of elasti obje ts is similar to gas expansion: it is a ompanied
8. Open the alorimeter and insert the obje t under study. Wait (by observing by thermal ee ts, heating or ooling. In this experiment we study thermal
the bridge readings) until the temperature of the alorimeter and the ee ts arising at adiabati stret hing of rubber. This substan e is spe ial
obje t omes to equilibrium. The a ura y of the measurement in reases sin e it ools at small deformations like ordinary substan es and heats up
if the temperature ranges used to determine the heat apa ity with and at large (although elasti ) deformations.
without the obje t oin ide. It is re ommended to get the obje t from the Consider the thermodynami relation
alorimeter after the temperature equalization and ool it under a stream
of tap water. Then dry the obje t with a soft tissue and also dry it under dU = T dS − δA, (1)
the jet of ompressed air from the pipeline. After that insert the obje t whi h follows from Eqs. (1.2) and (1.7).
into the alorimeter again, wait till the temperature equalizes, and do the Let a for e f be applied to a rubber band. The work δA done by the
measurements by repeating 47. The heating should last for 1520 minutes. band is the sum of the work done by the for e f (with opposite sign) and
Using the data determine the net heat apa ity C1 of the obje t and the the work of the band against the atmospheri pressure P :
alorimeter. The heat apa ity of the obje t is the dieren e CÒ = C1 − C0 .
9. Weigh the obje t and al ulate its spe i and the molar heat apa ity. δA = −f dl + P dV. (2)
Repeat the measurements for two or three obje ts. Here l is the band length and V is its volume. Rubber stret hing (as well as
stret hing of any elasti obje t) is a ompanied by a redu tion of its ross-
Questions se tion, so the volume does not hange mu h. Therefore the se ond term in
1. Give the denition of spe i and molar heat apa ity. Eq. (2) an be negle ted ompared to the rst. Then substituting Eq. (2)
2. What is the molar heat apa ity of a metal a ording to the lassi al theory? What into Eq. (1) one obtains:
is the molar heat apa ity of a hemi al ompound?
3. Des ribe the method used to redu e the error related to heat losses. dU = T dS + f dl. (3)
Literature A state of of the band like a gas state is determined by two quantities
1. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. II. Ì.: Íàóêà, 1990. 18, 63, 68.
whi h an be arbitrarily hosen. For the problem at hand it is onvenient
to take elongation and temperature as independent variables. Let us write
òîâàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 2, 2.2. Eq. (3) in these variables. To do this we add to and subtra t from the right-
hand side of Eq. (3) the quantity SdT :
ë. IX, 138. dU = T dS + SdT − SdT + f dl.
Ñ. 100102. The rst two terms are equal to d(T S). Moving them to the left-hand side
5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1. we obtain:
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 158. d(U − T S) = −SdT + f dl. (4)
The fun tion The se ond term of Eq. (9) an be repla ed by using Eq. (8). Substituting
F = U − TS (5) Eqs. (8) and (10) into (9) we obtain:

is alled Helmholtz free energy. Equation (4) shows that at onstant T ∂f
dT = dl. (11)
temperature (dT = 0) the work done by the for e responsible for reversible Cl ∂T l
stret hing equals the hange in the free energy, rather than in the internal
energy. The work an be equated to the hange of internal energy provided Thus we have found the relation between the band elongation and its
the entropy hange is negligible: temperature in rement. Equation (11) is valid for any obje t whi h undergoes
a reversible adiabati stret hing.
∂f
dFT = f dlT . (6) Now let us examine the fa tor ( ∂T )l . To maintain the onstant length of
an obje t at varying temperature one must balan e the thermal expansion
Now let us explore the mathemati al ontent of Eq. (4). It is the exa t by external ompression, i.e. by applying a ompression for e to the obje t.
dierential of fun tion F whi h depends on two variables, l and T . Therefore For ordinary substan e
∂f
< 0.
∂F ∂F ∂T l
S=− , f= . (7)
∂T l ∂l T One an see that the temperature variation of an obje t under deformation
2
is not surprising.
From the theory of real fun tion it is known that the se ond derivative ∂T
∂ F
∂l In the ase of a large elongation Eq. (11) must be integrated. Usually the
is independent of the order of dierentiation. Let us dierentiate the rst deformation related temperature in rement is small, so T an be repla ed
equation with respe t to l, the se ond with respe t to T , and equate the with onstant T0 ,
derivatives: Zl
∂f ∂S T0 ∂f
=− . (8) T − T0 = dl, (12)
∂T l ∂l T Cl ∂T l
l0
Re all that an entropy hange is related to the heat in rement as dS = and the integrand ∂f
( ∂T evaluated at T = T0 . Equation (12) is nal and an
)l
= δQ/T . Thus we have established the relation between thermal (the RHS) be used for al ulations providing the dependen e of f on l and T is known.
and dynami al (the LHS) properties of the band. This dependen e is taken from experimental data.
Instead of studying heat ex hange in isothermal pro ess one an explore For example, suppose that elasti properties of an obje t are des ribed
temperature variation of a thermally isolated obje t. If the pro ess is fast by Hooke's law and its thermal expansion is des ribed by the usual relation:
enough ompared to heat ex hange the thermal isolation is not ne essary.
In this ase the stret hing be omes adiabati or rather isentropi . In our l = l0 1 + α(T − T0 ) .
experiment
∂S

∂S We onsider the linear expansion oe ient α and the Young's modulus E
dS = dT + dl = 0. (9) be independent of temperature. It is not di ult to verify that in this ase
∂T l ∂l T
the expression for f is
The rst term in the RHS of Eq. (9) an be expressed in terms of the heat
l(f, T )
apa ity at onstant length, Cl . Indeed, f = Eσ0 −1 , (13)
l(0,T0 )[1 + α(T − T0 )]
(δQ)l = T (dS)l = Cl (dT )l . where σ0 is the area of the initial ross-se tion of the obje t. Indeed, T = T0
the ordinary Hooke's law is reprodu ed:
Therefore
∂S Cl ∆l
= . (10) f = Eσ0 .
∂T l T l0
If no external for e is applied the LHS of Eq. (13) vanishes and so does the For small ∆l/l this expression is dominated by the se ond term, so the
square bra ket on the right, so temperature de reases under stret hing. This is natural sin e moderate
rubber stret hing is well approximated by the ordinary Hooke's law whi h
l = l0 [1 + α(T − T0 )], a ording to Eq. (14) predi ts that temperature de reases under stret hing.
One an see that Eqs. (14) and (17) oin ide for small ∆l.
as to be expe ted. The oe ient of thermal expansion α is usually of the For large elongations the se ond term in the square bra kets of Eq. (17)
order of 10−5 ◦ C −1 , so α(T − T0 ) ≪ 1 and Eq. (13) an be written as: ex eeds the rst one, so the rubber heats up. The sign of thermal ee t for
most rubbers hanges at λ ≈ 1.10.
l
f = Eσ [1 − α(T − T0 )] − 1 . Let us briey explain why the thermal ee t hanges sign for rubbers
l0
unlike for ¾ordinary¿ elasti substan es: the internal energy of the latter
Substituting this expression into Eq. (12) we nd that grows with elongation while for rubber it remains onstant under stret hing
( ompare to the internal energy of ideal gas that depends only on its
αEσ0 T0 2 temperature but not on the volume).
∆T = − (l − l02 ). (14) Let us apply the se ond Eq. (7) to the isothermal stret hing of rubber
2Cl l0
(free energy F is dened by Eq. (5)): (5)):
Thus an elasti obje t whi h obeys Hooke's law and whi h E and α
are temperature independent ools under stret hing and heats up under f=
∂F
=
∂U
−T
∂S
≈ −T
∂S
.
ompression. This on lusion is in a ord with Chatelier's prin iple: any ∂l T ∂l T ∂l T ∂l T
hange in status quo prompts an opposing rea tion in the responding system.
The Young's moduli of aout hou and rubber depend both on elongation The elasti for e of rubber is due to hange of its entropy (not internal
and temperature. The relation between f , l and T an be des ribed by the energy!) under stret hing.
empiri al formula Rubber heating under stret hing an be understood by inspe ting its
mole ular stru ture. Polymer mole ules, whi h rubber is omposed of, are

E(T )σ0 1 + 3α(T − T0 ) long hains of arbon (or sili on) atoms folded into irregular lumps. These
f= λ− . (15) ¾ma romole ules¿ are atta hed to their neighbors by random hemi al
3 λ2
bonds. The bonds form during vul anization; large number of bonds makes
Here λ = l/l0 and σ0 is the initial ross-se tion of the sample. The Young's rubber rigid.
modulus of rubber is proportional to T : The ma romole ules parti ipate in thermal motion. If there is no
stret hing the mole ules move independently and the thermal energy
E = κT. (16) of ea h mole ule orresponds to the number of its degrees of freedom.
Under stret hing the ma romole ules an not move independently sin e the
To evaluate the temperature hange of a rubber band under stret hing stret hing for e organizes them into more rigid mole ules. The number of
we substitute Eqs. (15) and (16) into (12) and integrate. This gives degrees of freedom of the lumps be omes partially ¾frozen¿. Some part of the
thermal energy of the lumps is transfered to the thermal energy of mole ules
Eσ0 l0 2
∆T = T − T0 = (λ − 1) λ + 1 − (1 + 3αT0 ) . (17) and the temperature of rubber grows.
6Cl λ
The same on lusion follows from thermodynami reasoning. Stret hing
One an see that the band temperature de reases and then starts growing tends to orient the lumps of ma romole ules, i.e. omplete ¾disorder¿ of
as λ in reases. When λ is lose to one, we an substitute λ = 1 + ∆l/l. Then the polymer mole ular stru ture be omes partially organized. Ordering a
the square bra ket on the RHS of Eq. (17) be omes stru ture is equivalent to de reasing its entropy (re all that in kineti
theory entropy spe ies the degree of disorder of a system). Sin e the net

∆l entropy of the rubber band in our experiment must remain onstant, the
3 − 2αT0 . de rement of orientation entropy must be balan ed by in reasing the relative
l
1
11
2
PSfrag repla ements
ê Ô-116/1
3
2 1 3
PSfrag repla ements 10 Amplier Ô-116/1
4
Fig. 2. Lo ation of thermo ouple jun tions
P dierential hromel- opel thermo ouple (see Fig. 2). The diameter of the
thermo ouple wires is 0.14 mm. The hot jun tion 1 is lo ated inside the
9 band, the old jun tion is lo ated next to the band under a metal lamp.
5 The thermo ouple sensitivity is 64 µV/◦ C.
Maximum hange of the rubber temperature in this experiment is
several de imals of kelvin. Thus even a small dieren e between the initial
7 temperatures of the hot and old jun tions an signi antly ae t the
6 results. In order to better equalize the initial temperatures the band and
the thermo ouple are en losed in the asing whi h walls are overed with
8
aluminum foil. One should keep a light xture away from the asing and
do not tou h it otherwise a temperature gradient ould be reated inside
Fig. 1. Installation for studying thermal ee ts of the asing that in reases the initial emf. The thermo ouple lamps on the
elasti deformation of rubber band asing wall and on the amplier Ô-116/1 are overed with foam shields for
better thermal insulation. The shields should not be removed during the
haoti motion of dierent parts of the mole ules. In other words, the band experiment.
temperature will grow.
In a real experiment the stret hing is not perfe tly adiabati . Be ause of LABORATORY ASSIGNMENT
heat losses (irreversibility!) the measured value of ∆T is less than that one The experiment onsists of two parts. In the rst part the pro ess of
predi ted by theory. isothermal stret hing is studied; one veries Eq. (15) and measures the
Young's modulus. In the se ond part one studies the thermal ee ts during
Laboratory setup. The installation is shown in Fig. 1. Rubber band 1 is adiabati stret hing and ontra ting of the band.
xed by two lamps 3 and 11 and pla ed inside plexiglas asing 2. The upper
lamp is immobile while the lower one an move along two verti al rods 4. I. Measurement of band elongation versus the suspended weight.
The lower lamp position an be determined with the aid of ruler 10. A The weights are pla ed on the platform (see 1) lo ated outside the band
lightweight platform 5 lo ated outside the asing is atta hed to the lamp 3. asing.
The band is stret hed by weight P pla ed on the platform. Elongation of 1. Measure the band elongation by obtaining 68 experimental points for
the band is restri ted by stopper 7 whi h is xed on support 8 by s rews 6 1 6 λ 6 2.5. To ensure that a measurement is isothermal wait at least for
and 9 . two minutes after the pla ement of a new weight. Begin the measurements
Thermal ee ts due to rubber stret hing are measured by means of a with the heaviest weight whi h stret hes the rubber by the fa tor of 2.22.5.
put the platform onto the stopper 7 whi h has been preliminary xed at the
ln ∆T desired height.
7. Determine the value of ∆T0 for λ = 1.5; 2.0; and 2.5. The numeri al value
ln ∆T0 1
of α is 2.5·10−4 Ê−1 . Using your data and Eq. (17) evaluate Cl .
2
Questions
1. What onditions must be met to ensure that a deformation pro ess is reversible?
PSfrag repla ements 2. Show that Eq. (15) gives ordinary expressions for elasti stret hing and thermal
expansion at small values of λ and ∆T .
3. Is a rubber deformation without a thermal ee t possible?
Literature
òîâàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 2, 2.52.7.
0 t 2. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001.
Fig. 3. Dependen e of ln ∆T on time obtained for fast (1) and
Ñ. 126130.
optimum (2) stret hing of rubber band 3. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1.
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 191197.
2. Display the points on a graph by plotting the for e f on the abs issa and
λ − 1/λ2 on the ordinate. Verify that the graph is well approximated by
a straight line. (It is also useful to he k that the graph plotted in the 2.1.6. The JouleThomson ee t.
oordinates f , λ is not linear.) Using the plot nd the Young's modulus of
Purpose of the lab: 1) to determine temperature hange of arbon
rubber. The band size is displayed on the table next to the installation.
dioxide in pro ess of throttling through low-permeability partition at
various initial values of pressure and temperature; 2) to al ulate Van
II. Study of thermal ee ts a ompanying stret hing of rubber. der Waals oe ients ¾a¿ and ¾b¿ using experimental results.
3. Get the voltmeter Ô-116/1 ready for the measurement of thermo ouple
emf. Set the operation mode swit h in position ¾U¿, the operation range Tools and instruments: a tube with porous plug; a Dewar tube; a
at 750 µV , and turn on the power swit h. Let the voltmeter warm up for thermostat; thermometers; a dierential thermo ouple; a voltmeter; a
510 minutes. ballast balloon; and a pressure gauge.
4. Adjust the voltmeter sensitivity. To do this stret h the band during 1015 The JouleThomson ee t des ribes the temperature hange of gas
se onds (λ ≈ 2). The pointer deviation must be 7080% of the voltmeter slowly throttling from the area of high pressure to the area of low pressure
s ale. provided that no heat is ex hanged with the environment. In a rareed gas,
5. Remove the weight and wait till the temperature equalizes (about 3 whi h properties are lose to the properties of ideal gas, the temperature
minutes). remains onstant in this pro ess. The JouleThomson ee t illustrates the
6. Pla e the weight whi h stret hes the band by the fa tor of 22.5 on dieren e of an explored gas from the ideal one.
the platform 5. Inspe t how the band temperature hanges with time. In the lab one studies a temperature hange of arbon dioxide in the
Observations should be arried till the temperature equalizes. Plot the data pro ess of throttling through a tube with a porous partition (1). The tube 1
in the oordinates lg ∆T , t. By extrapolating the urve to the moment t = 0 is thermally insulated. The gas from the area of high pressure P1 is for ed
determine the value of ∆T0 . Noti e that if the band is stret hed too rapidly through a large number of narrow long hannels in the porous plug 2 to the
the studied dependen e an exhibit a narrow maximum orresponding to area of atmospheri pressure P2 . The pressure dieren e ∆P = P1 − P2 ,
os illations in the rubber (see Fig. 3). To avoid this it is re ommended to whi h is due to large resistan e of the hannels, ould be su ient even for
a low ow velo ity of gas. The size of JouleThomson ee t is determined to the ee t with opposite sign. If intera tion for es between mole ules are
a ording to the temperature dieren e of the gas before and after the plug. large enough, so that the ¾pressure orre tion¿ dominates, then the term
Consider a stationary ow of gas between any ross-se tions I and II of ontaining a makes the basi ontribution and
the tube (before the plug and after it). Suppose one mole of arbon dioxide
has passed through the tube, let µ be its molar mass. Let the molar volumes, ∆T
> 0,
the pressures and the internal energies per mole of gas in the ross-se tions ∆P
I and II be V1 , P1 , U1 , and V2 , P2 , U2 . To for e the volume V1 in the tube
i. e. the gas is ooled during the expansion (∆T < 0, sin e always ∆P < 0).
one should do the work A1 = P1 V1 . Passing through the ross-se tion II
In the opposite ase (small a)
the gas itself does the work A2 = P2 V2 . Sin e no heat and energy ex hange
takes pla e through the tube walls, ∆T
< 0,
µv22 µv12 ∆P
A1 − A2 = U2 + − U1 + . (1)
2 2 i. e. the gas temperature rises (∆T > 0, sin e ∆P < 0 as before).
In Eq. (1) one takes into a ount the hanges both in the internal energy One an understand the obtained result using an argument based on
(rst terms in the bra kets) and the kineti energy (se ond terms in the energy onservation. As we know the ideal gas does not exhibit the Joule
bra kets) of the gas. Substituting into Eq. (1) the expli it expressions for Thomson ee t. Intera tion energy of mole ules of ideal gas, ontrary to
A1 and A2 and regrouping one nds a real gas, an be negle ted. The intera tion energy results in ooling
or heating of real gases during an expansion. For large a the energy of
1 attra tion is great. Therefore the potential energy of mole ules de reases
H1 − H2 = (U1 + P1 V1 ) − (U2 + P2 V2 ) = µ(v22 − v12 ). (2)
2 during ompression and in reases during expansion. A gain in the potential
The quantity H in this expression is dened in Eq. (1.25). energy results in a loss of the kineti energy of mole ules and the temperature
Some remarks are due. First of all, noti e that in the JouleThomson of gas de reases during expansion. Similar arguments explain why for large
pro ess the gas experien es an appre iable fri tion in the porous plug, whi h values of b the temperature of expanding gas rises.
results in the plug heating. Energy losses due to the plug heating at the It follows from Eqs. (1.35) (1.36) that the oe ient µj−t be omes zero
beginning of the pro ess ould be signi ant and orrupt the observations. at the temperature Ti . Using the relation between the oe ients a and b
When the tube temperature be omes onstant, the gas arries away all the and the riti al temperature (1.19), one nds from Eq. (1.36) that
heat released in the tube and Eq. (1) be omes exa t. Of ourse, the tube
must be thermally well insulated, so that no heat es apes through its walls. 27
Tinv = Tcr . (4)
The se ond remark refers to the RHS of Eq. (2). The JouleThomson 4
pro ess per se takes pla e providing the RHS an be negle ted, i. e. the At Tinv the JouleThomson ee t hanges its sign: below the inversion
ma ros opi velo ity of gas before and after the plug is small enough. At temperature the ee t is positive (µj−t > 0, the gas ools) and above Tinv
the moment one doesn't have a quantitative riterion of this requirement. the ee t is negative (µj−t < 0, the gas heats up).
Therefore let us postpone the dis ussion of the problem on erning the right- The inversion temperature for all gases signi antly ex eeds the riti al
hand part of Eq. (2) and just assume that the gas enthalpy remains onstant one. For most gases Tinv /Tcr = 5 − 8. For instan e, for helium Tinv = 46 K,
a ording to Eq. (1.26). Tcr = 5.2 K; for hydrogen Tinv = 205 K, Tcr = 33 K; for nitrogen Tinv =
Consider Eq. (1.35): = 604 K, Tcr = 126 K; for air Tinv = 650 K, Tcr = 132.6 K; and for arbon
∆T 2a
−b dioxide Tinv = 2050 K, Tcr = 304 K. The inversion temperature for helium
µJ−T = ≈ RT
. (3) and hydrogen is signi antly below room temperature, therefore these
∆P Cp
gases heat up during expansion under standard onditions. The inversion
Equation (3) shows that the JouleThomson ee t for not very dense gas temperature of other gases is above room temperature and under standard
depends on the relation between the oe ients a and b, whi h ontribute onditions the gases ool during expansion.
Comparing the above values of Tinv and Tcr one an verify that
predi tions based on the Van der Waals equation for real gases are not quite v2
orre t. While representing the qualitative behavior of real gases orre tly, P2 Tâ Tê
the Van der Waals equation does not provide a fair quantitative des ription.
Ì
At large pressure dieren e, for example, in throttling from 200 to
1 atm (the integral JouleThomson ee t), as it is frequently used in Â
PSfrag repla ements v1
industrial installations, the expansion (1.28) is not appli able and the general P1
formula (1.26) should be used instead. The relation between temperature 5 atm CO2 from
pressure vessel
and pressure is determined from spe ial diagrams, for example, the urves
H = const, plotted in the oordinates of temperature pressure or
temperature entropy. Su h diagrams based on experimental data are widely
used in te hni al appli ations.
Now, ba k to the right-hand part of Eq. (2) and its inuen e on the
temperature dieren e of expanding gas. Let us ompare the temperature Thermostat
dieren e resulted from the JouleThomson ee t with the temperature

dieren e arising due to the hange in the kineti energy of gas1 . The Fig. 1. Installation for studying the JouleThomson ee t
in rement in the kineti energy of gas auses the appre iable and approximately
equal de rement of its temperature both for real and ideal gases. Therefore For arbon dioxide µ = 44 g/mol, Cp = 40 J/(mol·K), so
the ompli ated Van der Waals equation is not needed for the estimate .
Substituting in Eq. (2) U for CV T and P V for RT one obtains µ 44 · 10−3
∆T = (v22 − v12 ) = (1.42 − 0.282 ) = 7 · 10−4 K.
2Cp 2 · 40
(R + CV )(T1 − T2 ) = µ(v22 − v12 )/2,
This temperature dieren e is negligible ompared to the measured ee t
or (several kelvins).
µ In this experiment the JouleThomson oe ient for arbon dioxide is
∆T = (v 2 − v12 ).
2Cp 2 measured. The experimental results are then used to estimate the oe ient
of thermal expansion, the onstants in the Van der Waals equation, and the
In our experiment the gas ow rate does not ex eed 10 m3 /s and the tube
inversion temperature of arbon dioxide. The initial gas temperature T1 is
diameter equals 3 mm. Therefore
maintained by a thermostat. The measurements are arried out for three
4Q 4 · 10 m3 /s temperatures: room temperature, 50 ◦ C, and 80 ◦ C.
v2 6 = ≈ 140 m/s.
πd2 3,14 · (0.3)2 m2 Laboratory setup. The installation for studying the JouleThomson ee t
in arbon dioxide is shown in the gure. The prin ipal element of the
The ratio of the velo ities v1 and v2 of the gas entering the ork plug and installation is the tube 1 with the porous plug 2, through whi h the explored
exiting it equals the ratio of pressures P2 and P1 . In our installation P1 = gas is for ed. The length of the tube is 80 mm, the tube is made of stainless
= 4 atm and P2 = 1 atm, therefore steel whi h has a low thermal ondu tivity. The tube diameter is d = 3 mm,
the width of the walls is 0.2 mm. The porous plug is lo ated at the end of the
P2 1 atm tube and it is made of a porous glass with a large number of narrow and long
v1 = v2 = · 140 m/s = 35 m/s.
P1 4 atm hannels. The porosity and thi kness of the plug (l = 5 mm) are adjusted to
1 Here the kineti energy means the kineti energy of gas moving as a whole body. provide the optimal gas ow at the pressure dieren e ∆P 6 4 atm (the gas
Then v1 and v2 are the velo ities of ma ros opi gas motion. The obtained estimate shows ow rate is about 10 m3 /s), whi h results in an appre iable temperature
that it is mu h less than the thermal velo ity of mole ules. dieren e due to the JouleThomson ee t.
The pressurized arbon dioxide enters the tube through the oil 5 from Open the regulating valve V to set the value of the ex essive pressure
the bottle 6. The opper oil is immersed in water in the thermostat and ∆P ≈ 4 atm.
heats up the gas slowly passing through it to the thermostat temperature. 4. Wait 1015 minutes after opening the valve until transient pro esses de ay
The water temperature is measured by thermometer Tw pla ed in the and re ord the voltmeter readings.
thermostat. The required temperature is set and monitored by means of 5. By turning the valve V set the pressure 0.30.5 atm lower than the initial
the onta t thermometer Tc . one. Wait for about 5 minutes until the pressure and temperature dieren e
Gas pressure in the tube is measured by the manometer M and be ome onstant and re ord the readings of the manometer and voltmeter.
ontrolled by the valve V (by opening the valve V, i. e. by turning the
6. Carry out the measurements for several (57) pressure values at room
handle ounter lo kwise, one in reases the pressure P1 ). The manometer M
temperature.
measures the dieren e between the pressure inside the tube and the ambient
(atmospheri ) pressure. Sin e after passing through the porous plug the 7. Plot the dependen e ∆T (∆P ) and using the value of the slope determine
arbon dioxide enters the area with atmospheri pressure P2 , the manometer the JouleThomson oe ient at room temperature.
dire tly measures the pressure dieren e between the tube entran e and the 8. Upon nishing the measurements at room temperature lose the regulating
exit, ∆P = P1 − P2 . valve V and set the value 50 ◦ C on the onta t thermometer.
The dieren e of the gas temperature before and after the plug is 9. When the temperature will be ome onstant repeat the measurements of
measured by a dierential opper onstantan thermo ouple. A onstantan 37. When treating the results take into a ount that sensitivity of the
wire of 0.1 mm in diameter onne ts the joints 8 and 9, whereas opper wires opper onstantan thermo ouple depends on temperature as follows:
(of the same diameter) are onne ted to the digital voltmeter 7. The heat
es aping through the wire of su h a low ross-se tion is negligible. To redu e Temperature, ◦
C 010 1020 2030 3040 4050
m V/ ◦ C 38.9 39.8 40.7 41.6 42.5
the heat losses due to radiation the tube ontaining the porous plug is pla ed
in the Dewar vessel 3 with silver- oated walls. To redu e the heat losses due Temperature, ◦
C 5060 6070 7080 8090 90100
to onve tion the tube bottom is sealed with the gasket 4, the upper end m V/ ◦ C 43.3 44.1 44.9 45.6 46.4
of the tube is sealed with the plug 10 made of foam. Su h a plug produ es
10. Upon nishing the measurements at 50 ◦ C, repeat the measurements of 37
a negligible pressure dieren e between the inner hamber of the tube and
at 80 ◦ C.
the atmosphere.
11. Using Eq. (3) and the data obtained at three temperatures determine the
onstants a and b for arbon dioxide. Use two pairs of temperature values:
LABORATORY ASSIGNMENT room temperature and 50 ◦ C and 50 ◦ C and 80 ◦ C. Find the inverse
1. Before the experiment make sure that the thermostat is lled with water and temperature Tinv of arbon dioxide using Eq. (1.36).
all ele tri al devi es are grounded. One should remember that at the pressure 12. Compare the values obtained with the tabulated ones. Take into a ount
dieren es used in the installation (∆P 6 4 atm) the size of the ee t does that the tabulated values orrespond to the riti al temperature. Whi h
not ex eed 5 ◦ C (200 µV by voltmeter readings), so the installation is very of your results are loser to the tabulated values? What an you say about
sensitive to ele tri al and thermal disturban es. pre ision of the Van der Waals equation using the results of the experiment?
2. Using the onta t thermometer Tc set the temperature lose to the room 13. Estimate the errors.
temperature and turn on the thermostat.
3. Turn the swit h ¾Power¿ 11 on the voltmeter 7 in the position ¾On¿. Make Questions
sure that the voltmeter buttons ¾ACL¿ 12 (automati hoi e of the limit) 1. What is the dieren e between real and ideal gases?
and ¾U=¿ 13 (operation mode) are pushed. Write the sign and the value of 2. Plot the intera tion for e and the potential energy of two mole ules versus the
the voltmeter readings at ∆P = 0 (it an be non zero due to ele tromagneti distan e between them. Using the urves explain the JouleThomson ee t.
interferen e). Use this value as a referen e to orre t voltmeter readings in 3. Give the denition of riti al temperature. What is the inversion temperature?
the subsequent measurements: E = U (P ) − U (0). 4. Explain the sign of JouleThomson ee t for a = 0, b 6= 0 and for a 6= 0, b = 0.
52 THERMODYNAMIC PROCESSES
Literature Chapter II
1. General ourse of physi s. V. II. Thermodynami s and mole ular
TRANSPORT PHENOMENA
Sivuhin D.V.
physi s. M.: S ien e, 1979, 97, 98, 104.
ë. III, 111.
Ñ. 141151.
5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1.
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 197205.
Transport phenomena in gases

Chaoti thermal motion of mole ules transfer mass, momentum, and
energy. If the averaged value of one of these quantities varies along some
dire tion then transport of the orresponding quantity takes pla e: mass
transport is diusion, momentum transport is internal fri tion or vis osity,
and transport of energy results in thermal ondu tivity. From the kineti
theory perspe tive these phenomena are identi al, therefore it is onvenient
to onsider them simultaneously and derive the basi relations whi h reveal
distin t features of ea h kind of transport. To this end one has to introdu e
the basi parameters of gas: the velo ity of mole ular motion and the mean
free path.
Average velo ity of mole ular motion. During thermal motion gas
mole ules ollide, their velo ities hange, whi h leads the ensemble of
mole ules to statisti al equilibrium. In the equilibrium the velo ities are
distributed a ording to the Maxwell-Boltzmann distribution.
In the three-dimensional ase the distribution of velo ity magnitudes is
dN m 3/2 mv2
= 4π v 2 e− 2kT dv. (2.1)
N0 2πkT
In this relation N0 is the total number of mole ules, dN is the number of
mole ules with velo ities in the interval v , v + dv , m is the mole ular mass,
k is the Boltzmann onstant, and T is absolute temperature. The average
value of velo ity hvi is determined by summation of the produ ts of relative
number of mole ules and their velo ities:
Z
∞ r s
dN 8kT 8RT
hvi = v = = . (2.2)
N0 πm πµ
0
54 TRANSPORT PHENOMENA Chapter II 55
Here µ is the molar mass and k = 1.38·10−23 J/K is the Boltzmann onstant. onditions) n0 = 2.7 · 1019 m3 and Eq. (2.4) one an al ulate the ee tive
Noti e that the average velo ity of mole ules is lose to the speed of s attering ross-se tion σ = 6.2·10
p
−15
m2 whi h denes the kineti diameter
sound in gas c (1.17): of nitrogen mole ule as d = σ/π = 4 · 10−8 m. This means that at
s
r
γkT γRT standard onditions nitrogen mole ules travel on average the distan e λ =
c= = , (2.3) = 150d between two su essive ollisions.
m µ
where γ is the adiabati index whi h is equal to the ratio of the spe i heat The number of ollisions with wall. When studying transport phenomena
at onstant pressure to the spe i heat at onstant volume (see Eq. (1.12)). one should know the number of parti les rossing a unit area per se ond.
A ording to the lassi al theory of spe i heat (see Eq. (1.13)) the value To al ulate this number we use a simple approximation. During the time
of γ equals 5/3, 7/5, and 4/3 for monoatomi , diatomi , and polyatomi interval ∆t the mole ules travel the average distan e hvi ∆t. The mole ules
mole ules (the vibrational degrees of freedom are ignored sin e they are ontained in the ylindri al volume hvi ∆t∆S strike the area ∆S during
usually not ex ited at room temperature). Let us estimate the velo ities. the interval ∆t, the number of these mole ules is hvi ∆t∆Sn. Not all these
For air µ = 29 g/mol and at T = 293 K the average velo ity of mole ules mole ules rea h the area, but those whi h are moving toward the area.
equals hvi = 462 m/s, the speed of sound equals c = 343 m/s. A ording to Suppose that the distribution of mole ular velo ities is isotropi . There are
the above equations the average velo ity is always greater than the speed of three independent dire tions of motion. Then the number of mole ules whi h
sound. rea h the area equals 1/6 of the net number. Therefore approximately 16 n hvi
mole ules rea h a unit area per se ond. The pre ise value is 14 n hvi; however,
Mean free path. As it was already mentioned, gas mole ules do not move
using the methods whi h give this result to al ulate transport oe ients
freely all the time, sometimes they ollide with other mole ules. The mean
would ompli ate the derivations while the nal result turns out to be the
path traveled by a mole ule without ollisions is alled the mean free path.
same.
Let us denote this quantity by λ.
A spheri al mole ule of radius r an strike another mole ule during its
motion along a straight line if the enter of the se ond mole ule is lo ated Diusion, vis osity, and thermal ondu tivity of gases. Figure
at the distan e no more than 2r from the traje tory of the enter of the rst 2.1 summarizes the derivation of basi formulae of transport phenomena.
mole ule. On average this happens on e on the length λ. Therefore only one A transport pro eeds through the area lo ated along the axis x and
mole ular enter is lo ated in the ylindri al volume π(2r)2 λ, so perpendi ular to the axis z . Two additional surfa es lo ated at the distan e
λ from the area are plotted: 1 (below) and 2 (above) .
π(2r)2 λn = 1, We assume that approximately 16 n hvi mole ules ross a unit area per
se ond, where n is the number of mole ules per unit volume ( on entration),
where n is the mean number of mole ules per unit volume. From this relation and hvi is their mean velo ity.
we obtain
1 The diagrams on the gure orrespond to the ases when there are
λ= . (2.4) gradients of on entration, velo ity, and temperature. Basi laws of diusion,
σn
vis osity, and thermal ondu tivity are derived. The expressions for the
Here σ is the ee tive s attering ross-se tion. For spheri al mole ule σ =
orresponding transport oe ients are obtained in terms of mole ular
= π(2r)2 and equals the quadruple of its ross-se tional area. Equation (2.4)
parameters of the medium.
is an estimate whi h an be improved by taking into √ a ount the mutual
mole ular motion. This would bring an additional fa tor 2 in the denominator, Ea h transport oe ient is proportional to mole ular mean free path
however, for approximate al ulations this fa tor is not important due to λ; sin e this quantity is inversely proportional to the number of parti les
qualitative nature of the theory under onsideration. in a unit volume, the oe ients of vis osity and thermal ondu tivity are
For nitrogen at standard onditions (i. e. at the pressure of 760 mm. Hg. independent of the gas pressure. Of ourse, this on lusion remains valid
and the temperature of 0 ◦ C) the experimental value of λ = 0.6 · 10−5 m. while the mean free path is mu h less than the dimensions of ontainer.
Using Los hmidt's number (the number of mole ules in 1 m3 at standard Noti e also, that the oe ients of thermal ondu tivity and vis osity
are onne ted by the simple relation

z κ CV
Mass ow = ,
1 η µ
n2 hvi ∆M 1
n |6 {z } jz = = m hvi (n1 − n2 ) =
S∆t 6 where CV /µ is the spe i heat of gas at onstant volume. Experiment
λ 1 dn 1 dC onrms this relation although the numeri al oe ient turns out to be
x = − m hvi λ = − λ hvi ; C = mn; greater than unity: 1.32.5.
3 dz 3 dz
dC Besides the vis osity and thermal ondu tivity one often uses the
jz = −D . (2.5) oe ient of kinemati vis osity,
dz
λ
1 η
D = λ hvi .
(2.8)
z }| {
1 3 ν= ,
6 n1 hvi ρ
D is diusion oe ient.
and thermal diusivity,
κ
χ= . (2.9)
z Tangential stress ρ(CV /µ)
1
n hvi mvx2 ∆(M vx ) 1
Parameters D, ν , and χ have the same dimension (the SI unit is m2 /s)
vx |6 {z } τzx = = n hvi m(vx1 − vx2 ) = and a ording to the simple derivation given above all three oe ients are
S∆t 6
equal (experimentally they are of the same order and the above derivation
λ 1 dvx 1 dvx
x = − n hvi mλ = − λ hvi ρ ; shows that transport phenomena are of the same nature).
3 dz 3 dz The derivation is arried out in one-dimensional ase when on entration,
dvx
τzx = −η . (2.6) mass mole ular velo ity, and temperature depend on the single oordinate.
dz
λ In general ase these values an depend on two other dire tions meaning that
1
z }| { η = λ hvi ρ. the orresponding derivatives are nonzero. In that ase Eqs. (2.5) (2.7)
1 3
6 n hvi mvx1 should be also used for these dire tions. Ve tors of mass ux and heat ux
η is oe ient of vis osity.
are determined by gradient of on entration and temperature, respe tively:
j = −D grad C, q = −κ grad T, (2.10)

z Energy ux
∂ ∂ ∂
1 i
6 n hvi 2 kT2 ∆Q 1 i grad = i +j +k .
| {z } qz = = n hvi k(T1 − T2 ) = ∂x ∂y ∂z
T S∆t 6 2
Here i, j , k are unit ve tors along the axes x, y , z , respe tively.
λ 1 i dT 1 Cv dT
x = − n hvi kλ
3 2 dz
= − λ hvi ρ
3 µ dz
;
Stationary thermal ondu tivity. If the medium temperature is independent
dT of time, a transport problem is stationary. In the ase of axial ( ylindri al)
qz = −κ . (2.7)
dz symmetry, i. e. when T depends only on radius r, the temperature gradient
λ
1 Cv equals dT /dr and the heat ow density a ording to Eq. (2.7) is
z }| { κ = λ hvi ρ .
1 i 3 µ
6 n hvi 2 kT1 dT
κ is oe ient of thermal ondu tivity. q = −κ . (2.11)
dr
Fig. 2.1. Derivation of basi formulae of transport phenomena
Let us apply this equation to the installation in whi h the heat ux is
dire ted radially to ylinder walls from a lament lo ated along the ylinder
axis. The net heat ux Q equals the produ t of q and the area through whi h ree ted mole ules is the same, their mean energy is equal to one half of the
the ux passes, 2πrL, where L is the length of the ylinder and the lament: sum of their energies:
T1 + Tg
dT T1′ = .
Q = −2πrLκ . (2.12) 2
dr
Evidently this temperature is less than the temperature of the heated
Let us negle t the heat losses through the ylinder top and bottom and surfa e. It is this temperature whi h is a epted as gas temperature near
the heat transfer due to radiation. Then the stationary heat ux Q equals the heated surfa e. So, in this approximation there is the temperature jump
the joule heat released in the lament, it is independent of r and the equation ∆T near the surfa e of a solid body, whi h equals the temperature dieren e
an be easily integrated. To this end we multiply both parts of the equation of the gas and the body:
by −(2πLκ)−1 dr r : ∆T = T1 − T1′ . (2.14)
Q dr
dT = − . Using the above equations one obtains
2πLκ r
For onstant κ we obtain dT
∆T = g. (2.15)
Q r2 dr
T1 − T2 = ln . (2.13)
2πLκ r1
Noti e on e more that g , the oe ient of temperature jump, is of the same
Here r1 and T1 are the radius and temperature of the lament, r2 and T2 are order of magnitude as the mean free path, g ∼ λ.
the radius and temperature of the ylinder. This equation will be used in The given derivation of Eq. (2.15) is
the labs 2.2.2 and 2.2.3. based on a ommon assumption thatements
PSfrag repla the T
dieren e between the temperature T1 of
Temperature jump. When gas temperature drops the mean free path of the solid body surfa e and the extrapolated T1
gas mole ules be omes omparable with the diameter of heated lament, and ∆T
temperature T1′ is onsidered as the
this ompli ates the theoreti al des ription of heat transfer in its vi inity. ′
temperature jump, see Eq. (2.14). This T1
If there is a temperature gradient at the interfa e between solid body
value is al ulated using the relations whi h Tã
and gas, there is always a nite temperature jump next to the surfa e due to
are valid at some distan e from the surfa e, Tg g
niteness of the mean free path.
namely, Eq. (2.13) and the oe ient
At a distan e omparable with the mean free path one an assume that
of thermal ondu tivity. Therefore the
mole ules do not almost ollide with ea h other. ¾Hot¿ gas mole ules are
introdu ed temperature jump allows one r
moving away from the hot surfa e with the temperature T1 , whereas ¾ old¿
to redu e the ompli ated phenomenon of r1
mole ules are moving toward the surfa e; their temperature equals the gas
heat transfer near the surfa e to the simple Fig. 2.2. Gas temperature versus
temperature Tg at some distan e g from the surfa e, this distan e is of the distan e from lament surfa e:
variation of boundary ondition for gas
same order of magnitude as the mean free path. The parameter g is alled T1 lament temperature;
temperature.
the oe ient of temperature jump: Tã gas temperature near
Usage of the simple derivation is lament surfa e;
dT justied be ause no exa t theory of the T1′ extrapolated gas
Tg = T1′ − g. temperature jump exists up to date. One temperature near lament;
dr
ould expe t that su h a theory ould ∆T = T1 − T1 temperature
′
jump
Here T1′ is an extrapolated gas temperature determined below. Therefore be derived via numeri al solution of a
there are both ¾hot¿ and ¾ old¿ mole ules next to the surfa e of the solid ompli ated integro-dierential Boltzmann
body whi h are moving away and toward it, respe tively. In that region one equation. The hypothesized numeri al solution of the equation would be
should dene what the temperature means. Let us dene it as the mean ompli ated by the fa t, that not all mole ules are ree ted diusely from
energy of the ¾hot¿ and ¾ old¿ mole ules. Sin e the number of in ident and the surfa e, i.e. a quire the energy orresponding to surfa e temperature.
Part of the mole ules are elasti ally ree ted, i.e. with the same energy. A (2.7)) are not appli able to liquids and solids. In su h media the mole ules
relation between the numbers of su h mole ules ae t the value of g . are densely pa ked, i.e. lo ated side by side, therefore the on ept of mean
In the lab 2.2.2 the extrapolated temperature T1′ and the temperature free path, whi h is important in derivation of the orresponding relations
jump ∆T are determined by equating the heat ux, al ulated a ording for gases, is meaningless.
to Eq. (2.13), and the experimental value Q. In so doing the value of T1′ is Vis osity of liquid. A parti ular state of matter solid, liquid, or gas
substituted for T1 in Eq. (2.13) and the oe ient of thermal ondu tivity depends on its pressure and temperature. These parameters determine the
far from the lament is used. Thus, Eq. (2.13) is used as an extrapolation mean potential energy Ep of mole ular intera tion and the mean kineti
in the vi inity of lament (in the region r1 < r < r1 + λ), whi h allows one energy Ek of the mole ules. For solids |Ep | ≫ Ek : the for es of mole ular
to al ulate the heat ux a ording to Eqs. (2.11) and (2.12). intera tion are large enough and hold mole ules near equilibrium positions,
An approximate temperature dependen e on distan e in the vi inity latti e sites, despite their thermal motion. In gases the opposite takes pla e:
of lament is shown by the solid line in Fig. 2.2. In this area the law |Ep | ≪ Ek , therefore the mole ules move haoti ally and almost do not
of thermal ondu tivity (2.11) is not appli able, be ause the heat transfer intera t. The model of ideal gas orresponds to no intera tion limit.
o urs without ollisions between ¾hot¿ and ¾ old¿ mole ules. Therefore the For liquid both energies are omparable with the potential energy being
temperature hanges only slightly, while the heat ux is the same as that somewhat greater than the kineti energy: |Ep | > Ek . If in a solid ea h
one away from the lament. Equations (2.11) (2.13) are used to determine mole ule has the denite number of losest neighbors (depending on the
the onditional extrapolated temperature; it is shown by the dashed line in type of rystal latti e, for example, in lose pa king this number equals
Fig. 2.2 12), in the liquid state ea h mole ule loses one or two neighbors, so 910
Figure 2.2 shows that the al ulated temperature jump T1 − T1′ turns losest neighbors remain. Therefore the density of a simple liquid omposed
out to be less than the real temperature dieren e between a wall and of approximately spheri al mole ules in reases during solidi ation. (Noti e
gas. This is due to the fa t that the dependen e of temperature on that water whi h density de reases below the melting point is a polar
distan e a ording to Eq. (2.13) has positive urvature, whereas the real omplex liquid in whi h mole ular asso iations are formed.)
dependen e near the surfa e has negative urvature sin e in the region Unlike in solids, where mole ules os illate near the same equilibrium
where intermole ular ollisions are almost absent the spatial derivative of positions, in liquids due to weakened intermole ular bonds the mole ules
the temperature de reases. are held in equilibrium positions only for some time. Then due to thermal
One an noti e, that the temperature jump o urs near any solid surfa e motion and u tuations of kineti energy a mole ule jumps to the losest
at arbitrary value of pressure, if there is a gradient of gas temperature. possible equilibrium position at distan e about 10−8 m. To a omplish the
However, if the mean free path is less than a hara teristi dimension of the jump the mole ule must es ape from the potential well formed by the elds
problem at hand, so that the temperature dieren e along the mean free of neighbor mole ules. To surmount the energy barrier it has to do some work
path is negligible ompared to the hara teristi temperature dieren e, W alled a tivation energy. The value of W is the important parameter of a
the temperature jump an be ignored. For example, in the lab 2.2.2 the liquid. Low values of W orrespond to thin liquids and high values to very
temperature jump o urs not only next to the lament but near the ylinder vis ous liquids.
wall as well. A ording to Eqs. (2.15) and (2.12) the temperature jump near To estimate the number of mole ules whi h have the energy W , so they
the wall is less than near the lament, the orresponding ratio is r1 /r2 . For are able to over ome the resistan e of neighbors, let us employ a simple two
the installation used in the lab the ratio is about one over seven hundred level model. Let us assume that in a liquid there are only two mole ular
and ould be negle ted. states: one state orresponds to the net energy (the sum of potential and
kineti energy) W1 and the other state to energy W2 > W1 . A ording to
Transport phenomena in liquids and solids the Boltzmann distribution
Equations (2.5) (2.7) and (2.10) are also appli able to liquids and N2 e− kT
W2
e− kT
W2 −W1
W
solids. However mole ular transport in these media are signi antly dierent = W1 W2 = W2 −W1 ≈ e
− kT
. (2.16)
N1 + N2 e − +e − 1+e −
from the pro esses in gases, therefore the expressions for the oe ients of kT kT kT
diusion, vis osity, and thermal ondu tivity derived for gases (see Eqs. (2.5) Here N1 and N2 are the number of mole ules with energy W1 and W2 ,
respe tively, and W = W2 −W1 . In many liquids (water, al ohol) at standard Therefore the obtained formulae ould be orre t only in a limited temperature
onditions the dieren e W = W2 − W1 signi antly ex eeds kT , by a fa tor range. However the derivation takes into a ount the basi phenomenon
of three or more. Then the exponent in the denominator ould be ignored, responsible for the de rease of liquid vis osity at rising temperature, namely,
whi h has been done in Eq. (2.16). mole ular jumps over the potential barrier. The number of jumps in reases
Equation (2.16) gives the relative number of liquid mole ules whi h are with temperature and therefore the vis osity de reases.
able to make jumps. Noti e that gas vis osity is determined not by mole ular jumps, but by
Consider the me hanism of liquid deformation in some detail. The mole ular momentum transfer at the distan e equal to the mean free path
basi resistan e to deformation is due to low-mobile mole ules exe uting (see the derivation of Eq. (2.6)). Therefore gas vis osity has the opposite
os illating thermal motion near the same neighboring mole ules, like those dependen e on temperature: the gas vis osity in reases as the square root
in a solid. But unlike in a solid, there are mobile jumping mole ules in a of temperature due to in reasing average velo ity of mole ules. (Sin e the
liquid due to a small value of mole ular potential barrier. At any parti ular s attering ross-se tion de reases, be ause the ee tive mole ular attra tion
moment the number of su h mole ules is not large although every mole ule lessens as the temperature rises, the real gas vis osity in reases even faster).
has equal probability to jump, whi h happens some time later. This onvergen e of the properties is natural: as the temperature tends to
It is the displa ement by means of the jumps whi h is responsible for the riti al point, any dieren e between gas and liquid disappears.
relatively easy motion of a bulk of liquid subje ted to external for e. In this Heat equation. Consider a thin at element of a medium of unit area
ase the jumps o ur mainly in the dire tion of the applied for e, sin e it lo ated between x and x + dx, where the x-axis is perpendi ular to a heat
helps to surmount the potential barrier. The more jumps, the more liquid ux. The dieren e between the uxes oming into the element is equal to
moves, therefore, the less vis osity. The latter is onsidered as the ause of ∂q ∂q
∂x dx; for a small time period dt the element loses heat − ∂x dxdt and the
resistan e to motion when the liquid is des ribed as a ontinuous medium. orresponding temperature in rement an be found by equating the heat to
One an on lude from the above dis ussion that the oe ient of vis osity
∂t dtdx (where ρcV is the spe i heat apa ity per unit volume). Using
ρcV ∂T
must be inversely proportional to the number of parti les whi h are able to the relation between the heat ux and the temperature gradient (2.7), one
surmount the energy barrier W . Then it follows from Eq. (2.16) that the obtains the heat equation
vis osity oe ient liquid is
∂T ∂ 2T κ
W =χ 2, χ= . (2.19)
η = Ae kT . (2.17) ∂t ∂x ρcV
In the simple model onsidered the oe ient A does not depend on Here χ is the thermal diusivity measured in m2 /s (in SI), whi h follows
temperature, therefore in this approximation the a tivation energy W ould from the partial dierential equation sin e the units of the left- and right-
be easily determined from the experimental temperature dependen e of η . hand sides should be the same.
A ording to Eq. (2.17) the plot of the vis osity logarithm ln η versus 1/T It follows from the dimensional onsideration that the partial dierential
must be a straight line whi h slope determines the a tivation energy of the equation (2.19) has a solution whi h depends only on a dimensionless
2
mole ules: ombination of x, t, and χ, e. g. on β = xtχ . This an be veried by
d(ln η) substituting this solution into Eq. (2.19). This results in the ordinary
W =k . (2.18)
d(1/T ) dierential equation of the se ond order whi h ontains only the value of
Analyzing a deviation of the plotted urve from the straight line one ould β and the temperature T whi h depends on it. The solution an be written
estimate the validity of the approximation. as an integral, whi h an be al ulated numeri ally. It is important that
Experiment shows, that in small temperature ranges Eqs. (2.17) and (2.18) dierent temperatures orrespond to dierent values of β . For example, set
des ribe the temperature dependen e of vis osity quite well. The agreement β = 1. Then
is worse for a wide temperature range, whi h is to be expe ted: the x2 = tχ. (2.20)
equations are derived for a simple model of liquid without taking into This implies that ertain temperature orresponds to ertain oordinate
a ount mole ular omposition and stru ture and possible phase transitions. x whi h varies in time a ording to Eq. (2.20). The temperature an be
64 TRANSPORT PHENOMENA 2.2.1 65
found from the exa t solution of the dierential equation. For example, in
the problem of heating a old half-spa e by a hot wall at x = 0 held at
onstant temperature, Eq. (2.20) approximately orresponds to the half-
sum of the hot and old temperatures. It is onvenient to use Eq. (2.20) to
estimate the time of heating in problems with simple geometry, e. g., when
estimating the time of plate heating in the lab 2.2.4.
2.2.1. Experimental study of mole ular diusion

of gases atm
dispenser
Purpose of the lab: 1) to measure helium on entration in air as a
fun tion of time at various initial pressures by means of dete tors of S.C.
thermal ondu tivity; 2) to determine diusion oe ient using the data.
Tools and instruments: an experimental installation; a low va uum

pump; a helium gasometer; a manometer; a urrent sour e; a resistan e fore pump
de ade box; a galvanometer; and a stopwat h. helium
Diusion is a haoti propagation of mole ules be ause of their thermal

motion. Diusion in liquids is faster than in solids, and diusion in gases Fig. 1. Installation for studying mole ular diusion
is faster than in liquids. Diusion of mole ules of the same kind is alled
self-diusion, and diusion of mole ules of dierent kinds is alled hemi al diusion ow through any ross-se tion is the same. Therefore J = −DS ∂n
∂x
diusion. remains onstant throughout the tube. Then
Figure 1 shows an installation that allows one to study hemi al diusion
of gases and determine the diusion oe ient. Two glass ontainers of the n1 − n2
J = −DS . (2)
volumes V1 and V2 are onne ted by a tube of length l and ross-se tion l
S . The ontainers are lled with mixture of air and helium with dierent
Let ∆n1 and ∆n2 be the in rement of on entration in the volumes V1
hemi al omposition and the same pressure. The on entrations of the gases
and V2 for the time ∆t. Then V1 ∆n1 and V2 ∆n2 is the in rement of the
in the ontainers gradually equalize be ause of mole ular diusion.
gas omponent in V1 and V2 , respe tively. Due to onservation of matter
Let us onsider the pro ess of equalization in some detail. Suppose that
V1 n1 + V2 n2 = const, when e V1 ∆n1 = −V2 ∆n2 . The in rements are due to
the on entration of a gas omponent in the ontainer V1 is n1 and in V2
diusion, so
it is n2 . The density of the diusion ow of a gas omponent (i.e. the
number of mole ules rossing the unit area per se ond) is determined by n1 − n2
Fi k's law (2.5): V1 ∆n1 = −V2 ∆n2 = J∆t = −DS ∆t. (3)
l
∂n
j = −D , (1) Dividing this equation by ∆t, one obtains:
∂x
where D is the diusion oe ient and j is the ow density. In our ase dn1 n1 − n2 dn2 n1 − n2
the solution of the equation is simplied be ause: a) the volume of the tube V1 = −DS , V2 = DS . (4)
dt l dt l
onne ting the ontainers is small ompared to their volumes and b) the gas
on entration in a ontainer an be onsidered uniform . The density of the Now, dividing the rst equation by V1 , the se ond one by V2 , and subtra ting
them one gets: In this experiment the on entration is determined via the measurement
of the thermal ondu tivity of gas mixture with the aid of the dete tors
dn1 dn2 n1 − n2 1 1 D1 , D2 (1) and then using the dependen e of thermal ondu tivity of the
− =− DS + . (5)
dt dt l V1 V2 mixture on its omposition. A thin wire of radius rw stret hed along the
glass ylinder of the radius Rc is heated by ele tri urrent. The produ ed
Introdu ing the new variable n1 − n2 one an easily integrate the obtained
heat is then transferred to the ylinder walls mostly due to the thermal
equation:
ondu tivity of the gas inside. The rate of the heat transfer an be obtained
n1 − n2 = (n1 − n2 )0 e−t/τ , (6)
from Eq. (2.13):
where (n1 − n2 )0 is the dieren e of the on entrations at the initial moment 2πL
Q=κ (T1 − T2 ), (8)
and ln(Rc /rw )
V1 V2 l
τ= . (7) where κ is thermal ondu tivity, L is the length of the wire, and T1 and
V1 + V2 SD
T2 is the temperature of the wire and the wall, respe tively. The dissipated
power is maintained onstant (Q = const), so the wire temperature (and
therefore its resistan e) is determined by the thermal ondu tivity of the
gas and therefore by its hemi al omposition.
The dieren e of the on entrations is measured by means of the bridge
ir uit shown in Fig. 2. Here D1 and D2 are the dete tors of thermal
ondu tivity lo ated in the ontainers V1 and V2 . The resistors R1 , R2 ,
and R are used to balan e the bridge. A galvanometer is onne ted in series
with one of the bridge legs, the other leg has a sour e of dire t voltage.
When the ontainers are lled with the same mixture of gases one balan es
fine the bridge, so that a subsequent hange in the hemi al ompositions of the
balancing mixtures unbalan es the bridge. The magnitude of the unbalan e depends
on the on entration dieren e.
The dependen e of thermal ondu tivity of gas mixture on its hemi al
coarse omposition is a ompli ated fun tion. However it is reasonable to expe t
balancing that for a small dieren e in the on entrations, the urrent through the
galvanometer G is proportional to the dieren e (the rst term of the Taylor
series). Experiment shows that for a dieren e of 15%, the orre tion to
the linear approximation does not ex eed 0.5% that would su e for our
experiment.
During diusion the on entration dieren e de ays in a ordan e with
Eq. (6). The galvanometer readings follow the same law, i.e.
N = N0 e−t/τ , (9)
Fig. 2. Bridge ir uit with thermal ondu tivity dete tors for
measuring gas on entration
where N0 is the initial reading.
Equation (6) shows that the dieren e of the on entrations de ays exponentially
with time and the de ay rate is inversely proportional to τ (the de ay Some features of the experimental setup are worth dis ussing.
onstant). The latter is determined by the installation geometry (l, S , V1 , 1. To minimize onve tion the dete tor is made of a long glass tube with
and V2 ) and the diusion oe ient D. a platinum wire stret hed inside. The tube inner volume is onne ted to
the ontainer via several openings. The size of the openings is hosen so onne ted to the dispenser. The handle (see Figs. 1 and 3) (shadowed area)
that the diusion rate from the ontainer to the tube signi antly ex eeds is in the quadrant I. To release the helium into the installation the handle
the rate of diusion between the ontainers. Thus the hemi al omposition should be turned to the quadrant II. The pro edure is repeated several times
of the gas inside the dete tor is pra ti ally the same as that one in the until there is enough helium in the installation. Extra helium, if any, an be
ontainer. 2. Sin e the energy ex hange between the gas mole ules and the removed from the installation by the va uum pump. The design of valve Ê6
wire surfa e is not perfe t, the wire temperature is somewhat higher than the is not identi al in dierent installations but the operation prin iple is the
temperature of the adja ent gas layers (see the lab 2.2.2). The magnitude of same: helium is released by small portions.
the temperature drop depends on pressure. Be ause of that and also be ause The valve Ê4 is made spe ially airtight while the valve Ê6 is not.
the dete tors are not identi al, the bridge balan e depends on pressure to Therefore the valve Ê4 must be shut upon lling the volumes V1 and V2
some extent. To redu e the error it is re ommended to balan e the bridge in order to maintain a onstant pressure during the experiment.
at the pressure lose to the operation value. The ele tri ir uit of the installation is shown in Fig. 2. D1 and D2 are
Laboratory setup. The installation s heme is shown in Fig. 1. The ele tri the resistan es of the pressure dete tors, they form one leg of the bridge. The
se ond leg in ludes the resistan es r1 , R1 and r2 , R2 . The values r1 ≪ R1 and
ir uit is shown in Fig. 2. Figure 3 shows the s heme of valve Ê6 .
r2 ≪ R2 . Potentiometers R1 and R2 are oupled, their sliding onta ts are
The installation onsists of two ontainers V1 and V2 onne ted by the
xed on the same axis. They are used for the oarse balan ing of the bridge.
valve Ê3 , a va uum pump with the swit h T, the manometer M, and a
The ne balan ing is performed by potentiometer R. The resistan e de ade
helium supply line onne ted to the installation by the valves Ê6 and Ê7 . The
valve Ê5 onne ts the pump either to the installation or to the atmosphere. box MR is onne ted in series with the galvanometer . When balan ing the
bridge the resistan e of MR must be set to zero. On the other hand, when
A safety ontainer Ï.Á. is inserted between the pump and the valve Ê5 to
prote t the installation from a possible spillage of the oil from the pump. omposing the gas mixture the bridge is unbalan ed and MR must be set to
The ontainers V1 and V2 an be onne ted either to the helium supply line maximum resistan e to prevent the galvanometer from burn out.
or to the pump by using the valves Ê1 , Ê2 , Ê4 , and Ê5 . The manometer M LABORATORY ASSIGNMENT
measures the pressure in the ontainers.
1. Familiarize yourself with the installation.
The pressure of helium in the line
2. Turn on the power supply by swit h B (see Fig. 2). Open the valves Ê1 , Ê2 ,
ex eeds the atmospheri pressure. This
and Ê3 (see Fig. 1).
to the installation is ne essary to ensure purity of helium
3. Eva uate the installation. To this end open the valve Ê4 . Turn on the va uum
in the line if an a idental leak o urs.
pump (Ô.Í.) by the swit h T on the pump asing and onne t the pump
Any system of helium supply has leaks,
to the installation by turning the long handle of the valve Ê5 to the left (to
in our installation the valve Ê6 is
dispenser the installation). The pump should ontinuously operate at least 35 min
espe ially vulnerable. The valve Ê7 is
stopper to a hieve the pressure of ∼0.1 torr.1 To terminate the pumping turn the
installed to preserve helium and to redu e
plug long handle of the valve Ê5 upward. If you turn o the pump the handle of
an un ontrollable helium leakage into
the valve Ê5 must be turned to the right, this would onne t the pump to
the installation via the valve Ê6 . The
the atmosphere. Otherwise the oil from the pump an be spillied into the
valve Ê7 should be open only when lling
installation, whi h will require lean-up.
the installation with helium. During the
helium experiment the valve must be shut. 4. Then ll the installation with air (at rst, at P ∼ 40 torr) in order to
The dispenser on the valve Ê6 installed balan e the bridge at the operational pressure. To do so turn the handle of
Fig. 3. Valve Ê6 between the valves Ê7 and Ê4 serves to the valve Ê5 from the right position (air enters the pump) to the left position
supply helium to the installation by small (the air from the pump enters the installation). This operation should be
amounts. The dispenser itself is a small volume to be lled with helium whi h repeated several times until the required pressure is a hieved. If the pressure
is then released to the ontainer by the valve Ê6 . The ross-se tion of the is too high, the extra air an be removed by the pump.
valve Ê6 is shown in Fig. 3.One an see how the helium supply line an be 1 1 torr = 1 mm Hg= 133 Pa.
Balan e the bridge. Begin the balan ing at the resistan e MR ∼ 105 Ohm range of 3050% of the galvanometer s ale (whi h is proportional to the
by using the knob ¾ oarse¿ (2) and gradually de reasing the resistan e of MR dieren e in on entrations). Not less than 10 points should be re orded.
to 0, then use the knob ¾ne¿. The nal balan ing should be performed in 7. Continue the measurements (a ording to 36) at various (34) values of
the galvanometer measurement range of 1 µA. When the bridge is balan ed Pwork in the range of 40400 torr.
the resistan es should be set to maximum. This must be done to prevent 8. Verify the law of diusion (6). To this end plot the graphs for ea h value
the galvanometer from a idental burn out during the experiment. The of the pressure by plotting time on the abs issa and the logarithm of the
galvanometer measurement range should be set at 10 µA. galvanometer readings on the ordinate. The points must lie on straight lines.
5. Fill the ontainer V2 and V1 with air and an air-helium mixture, respe tively. Using the values of the slopes and the installation parameters al ulate the
The lling pro eeds as follows: diusion oe ients at the hosen pressures.
a) Eva uate the installation to the pressure of ∼0.1 torr. 9. Plot the diusion oe ient D versus 1/P . The points must lie on a straight
b) Shut the valves Ê2 and Ê3 and make sure that the valves Ê1 and Ê4 line. Cal ulate the diusion oe ient at the atmospheri pressure.
are open. 10. Using the data estimate the mean free path and the size of mole ules.
) Fill the volume V1 with helium until the pressure be omes 0.1 Pwork ,
i.e. to ∼4 torr. The pressure in the supply line is above the atmospheri Questions
pressure and, therefore, mu h greater than 4 torr. Therefore it is not allowed 1. Show that in the installation the on entration of gases an be onsidered uniform
to onne t the supply line and the installation dire tly. At rst, helium in the whole volume of V1 (and V2 ).
lls the dispenser (a small volume) and then the dispenser is onne ted to 2. Why is the dependen e of D on 1/P expe ted to be a straight line?
the installation volume (see Fig. (3). This is done repeatedly by turning Literature
the handle of the valve Ê6 from position I to position II until the required 1. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. II. Òåðìîäèíàìèêà è ìîëåêóëÿðíàÿ
pressure is a hieved. If the pressure is too large extra helium an be removed èçèêà. Ì.: Íàóêà, 1979. 90, 92, 93.
by the pump. It is re ommended to remove the helium ompletely and then 2. Áåëîíó÷êèí Â.Å., Çàèêèí Ä.À., Öèïåíþê Þ.Ì. Îñíîâû èçèêè. Ò. 2. Êâàíòî
ll the installation again to ensure the helium purity. When the ontainer âàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 1, 1.2, 1.3.
V1 is lled with helium, the valve Ê1 must be shut and the rest of helium ë. 2, 2.5.
must be eva uated from the installation till the pressure of ∼0.1 torr). 3. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976.
d) Open the valve Ê2 and ll the ontainer V2 with air till the pressure ë. III, 40, 42, 43.
of ∼ 1.5 Pwork . Then shut the valve Ê4 . This should be done be ause this 4. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001.
valve is airtight unlike the valves to the right, espe ially Ê6 . Ñ. 7880, 8792.
e) Equalize the pressure in V1 and V2 by opening the valve Ê1 with Ê2 5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1.
already opened (the valve Ê3 must be shut). Do not rush to open the valves Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 231233.
Ê1 and Ê2 be ause of adiabati expansion/ ompression taking pla e in the
ontainers. Be ause of that the temperature in one of the ontainers goes
up and in the other one goes down. The initial state must be isothermi . So,
during equalization of the temperature and pressure get the measurement
part of the installation ready to work. For this purpose, gradually de rease
the resistan e of MR until the galvanometer hand deviates from the neutral
position by ∼95% of the s ale. If the deviation is small even at MR = 0, the
sensitivity should be in reased from 10 µA to 5 µA, or to 1 µA. If this task
takes more than 12 minutes, shut the valves Ê1 and Ê2 and then ontinue
to adjust the galvanometer.
6. Do the measurements. Open the valve Ê3 , start the stopwat h and re ord
the galvanometer readings versus time. The measurement should span the
2.2.2. Measurement of thermal ondu tivity of T
air at various pressures
Purpose of the lab: 1) to study heat transfer from a heated lament T = Tf
to a ylindri al shell by rareed air; 2) to determine air temperature
PSfrag repla ements
near the lament assuming that the oe ient of thermal ondu tivity T ′ = Tr
remains onstant with distan e; 3) to al ulate the dieren e between
the temperature next to the lament and the measured temperature of
its surfa e; 4) to determine the dependen e of this dieren e, i. e. the
temperature jump, on pressure. T ′ = TR
T = Tc
Tools and instruments: an installation for measuring thermal
x
ondu tivity of gas; a va uum pump; a manometer; a va uum gauge; a
0 x=r x=R
double Wheatstone bridge; a rheostat; a galvanometer; an ammeter; and
a sour e of dire t voltage of 34 V. Fig. 1. Temperature jump near lament surfa e (x = r ) and
ylinder wall (x = R)
If the temperature of a gas ontained in a vessel is not uniform then Temperature gradient in the vi inity of a wall is not ontinuous be ause
some pro esses emerge whi h tend to equalize the temperature. At standard the me hanism of heat transfer between gas mole ules and wall mole ules
onditions the pro ess of onve tion plays the major role. Conve tion arises diers from that one between gas mole ules. The oordinate dependen e of
be ause a par el of light warm gas moves up while a older par el moves gas temperature lose to a wall is ompli ated, whi h is illustrated in Fig. 1
down on its pla e. Conve tion does not o ur if the gas temperature grows (T is a wall temperature and T ′ is an extrapolated gas temperature).
with height, or if the gas volume is not large enough, or if the volume is In theoreti al onsideration of this issue one usually extrapolates the
divided into small hannels or ells. In the last two ases a onve tion ow oordinate dependen e of gas temperature up to the wall and nds some
is impeded by vis osity. temperature T ′ . The dieren e between T and T ′ is alled temperature
The absen e of onve tion slows down heat transfer but does not stop jump. Thus, instead of taking into a ount the temperature jump, the
it ompletely. The transfer pro eeds by means of thermal ondu tivity of temperature dependen e is onsidered regular and the wall temperature T
gas due to thermal motion of its mole ules. The temperature equalization is is substituted by T ′ .
attained via ontinuous mixing of ¾hot¿ and ¾ old¿ mole ules, whi h is not The rigorous theory of temperature jump is still la king. However one
a ompanied by a ma ros opi ow of gas. It is this ase whi h is studied in an make some assumptions justied by experiment. The ¾anomalous¿
our experiment. temperature dependen e o urs in the region whi h width is of the same
In an axially symmetri al assembly, in whi h a heat ow is dire ted order of magnitude as the mole ular mean free path λ. The mole ules
radially from a lament to a ylinder wall, Eq. (2.13) is valid: separated from the wall by the distan e ex eeding several λ do not strike
it and ollide only with ea h other. The heat transfer at su h distan e is
Q R
Tr − TR = ln . (1) the same as in the bulk of gas. Therefore one an expe t the temperature
2πLκ r jump to be proportional to the width of the anomalous region, i. e. to λ,
Equation (1) an be used to determine κ . To this end one should know the and onsequently to be inversely proportional to P . Besides, it is lear that
lament and ylinder radii, r and R, the ylinder length, the heat ux, and there is no jump if there is no temperature gradient. The simplest formula
the temperature dieren e between the lament and the ylinder. that takes into a ount both observations is
The lament is heated by ele tri urrent. In the stationary regime the A dT
heat ux Q equals the Joule heat dissipated in the lament. The Joule heat ∆T = T − T ′ = , (2)
P dx
an be easily determined from the lament resistan e and the urrent. The
prin ipal di ulty is measurement of the temperature dieren e. where A is a oe ient whi h depends on the gas omposition and also on the
wall material and stru ture. Equation (2) is well onrmed by experiment. the ordinate equals the rst term on the right hand side of Eq. (9). Using it
Thus we on lude that Tr and TR in Eq. (1) are not the wall temperatures one an easily nd1 κ .
but rather the temperatures plus the temperature jump orre tion: Finally let us return to Eq. (2.12) whi h determines the temperature
distribution in the ylinder. This formula an be written as
Tr − TR = (Tf − ∆Tf ) − (Tc + ∆Tc ) = Tf − Tc − (∆Tf + ∆Tc ), (3)
dT Q 1
=− . (10)
where Tf and Tc are the lament and ylinder temperatures and ∆Tf and dx 2πLκ x
∆Tc are the orresponding temperature jumps.
The temperature gradient in the lament vi inity, where x is small, is tens
Let us write the temperature jumps using Eq. (2):
maybe hundreds times greater than near the ylinder surfa e.
" # The major variation of the temperature o urs near the lament, a tually
1 dT dT
∆Tf + ∆Tc = Af + Ac . (4) at the distan e of several lament radii. Therefore the most abrupt hanges
P dx f dx c of the heat transfer me hanism o ur in the pressure range in whi h the
mole ular mean free path approa hes the lament radius. This pressure
Repla ing (dT /dx)f and (dT /dx)c using Eq. (2.12) one obtains: range should be thoroughly studied in the experiment.

dT

Q 1

dT

Q 1 Laboratory setup. The experimental installation is shown in Fig. 2. The
= , = . (5) measurement unit onsists of a glass ylinder with a lament lo ated on
dx 2πLκ r dx 2πLκ R
f c its axis and heated by ele tri urrent. The lament diameter is about
0.05 mm, and the ylinder diameter is 1.5 m. The exa t values are written
Substituting Eq. (5) into Eq. (4) and then into Eq. (3) one nds
on the installation. The gas used in the experiment is air. The ylinder is
1 Q

Af Ac
onne ted to a va uum pump. The air pressure in the ylinder is measured
Tr − TR = Tf − Tc − + . (6) by indi ator manometer M used for relatively large pressures and by a U-
P 2πLκ r R
shape oil manometer used for low pressures. The s ale zero of the pressure
Now let us divide this equation by Q and noti e that the oe ient at 1/P gauge M orresponds to the atmospheri pressure in the ylinder.
does not depend on gas pressure. Let us denote this oe ient by B : The lament temperature is determined via its resistan e. The resistan e
is measured by a double Wheatstone bridge.
1 Af Ac The double bridge is used to measure low resistan es and allows one
B= + . (7)
2πLκ r R to redu e signi antly the errors due to resistan es of the onne ting wires
and onta ts. The ir uit diagram of double bridge is shown in Fig. 3. Here
Then RN , Rx , R2 , and R1′ are the resistan es of the bridge bran hes, R3 , R1 are
Tr − TR Tf − Tc B
= − . (8) the resistan es of the double bridge bran hes, and R are the resistan es of
Q Q P jun tions and wires in the ir uit RN , Rx . Assuming that the resistan es
Substituting Eq. (8) into Eq. (1) one nds: of jun tions and wires are in luded in the values of the orresponding
resistan es one denes the ondition of bridge balan e as:
Tf − Tc 1 R B
= ln + . (9) IN RN + I3 R3 = I2 R2 ,
Q 2πLκ r P
I1 R1 + Ix Rx = I1′ R1′ , (11)
All quantities in Eq. (9) ex ept for B and κ an be dire tly measured. I3 R3 + I1 R1 = IR R.
The terms ontaining κ and B an be determined from experimental data. 1 Stri tly speaking Eqs. (2.11) and (9) are valid providing the mole ular mean free
To do this one should arry out the measurements at dierent P . The results path is less than the hara teristi dimensions of the installation in luding the lament
are then plotted in the oordinates 1/P and (Tf − Tc )/Q. The experimental diameter. A more thorough analysis shows that Eq. (9) persists even when the ondition
points must lie on a straight line whi h slope equals B . The inter ept with λ ≪ r is no longer valid.
atmosphere
IN IR Ix
B
A
RN R Rx
Va 1 I3 I1
C
R3 R1
pump Γ
I2 I1′
R2 D R1′
Va 2
Fig. 3. Cir uit diagram of double Wheatstone bridge used for
measuring lament resistan e
Va 3 resistan e Rx be omes
RN R1′
Rx = . (14)
R2
Rx In our experiment a standard bridge -329 is used. In this bridge the
resistan es R1 and R1′ are onne ted to the same swit hes therefore equation
R1 = R1′ is always valid. Setting R2 = R3 on the upper panel of bridge
-329 using plugs, one ensures that Eq. (13) is satised. To redu e the
error due to resistan es of onne ting wires and jun tions the value of R
should be made as small as possible whereas the resistan es R1 , R1′ , R2 , and
R3 should be made as large as possible. Usually one hooses R1 , R1′ , R2 ,
and R3 > 10 Ohm.
switches On the lower part of the bridge front panel there are buttons ¾Roughly¿,
¾Pre isely¿ and ¾Damping¿ . Pressing the button ¾Roughly¿ one onne ts
the galvanometer to the bridge diagonal in series with a large resistan e,
coarse fine damping pressing the button ¾Pre isely¿ onne ts the galvanometer to the diagonal
dire tly. Pressing the button ¾Damping¿ one dis onne ts the galanometer
Fig. 2. Installation for measuring thermal ondu tivity of air from the ir uit and onne ts it to a small resistan e, whi h results in a rapid
damping of its os illations. To balan e the bridge one presses the button
Sin e at the balan e IN = Ix , I3 = I1 , I2 = I1′ , and IR = IN − I3 , ¾Roughly¿ and de reases galvanometer readings as mu h as possible, then
′ presses the button ¾Pre isely¿ and does the same. One must not press two
R1′ RR3 R1 R1 or more buttons simultaneously.
Rx = RN + − . (12)
R2 R + R3 + R1 R2 R3 The urrent supplied by battery B serves both to heat the lament
and to power the bridge. The battery is onne ted to diagonal AB. A
If the ondition
resistan e de ade box r is used to ontrol the urrent through the lament
R1′ R3 = R1 R2 , (13)
and galvanometer G is used to measure this urrent. The diagram shows that
is satised the se ond term of the equation vanishes and the unknown not all urrent measured by the galvanometer passes through the lament.
It an be veried that well: a greater urrent orresponds to greater sensitivity. Therefore if the
urrent in reases the galvanometer readings at rst do not de rease but
R1′ + R2
Ix = I, (15) rather in rease. Further in rease of the urrent results in the signi ant
Rx + RN + R1′ + R2 in rease of the lament temperature and onsequently redu es the unbalan e.
where Ix is the urrent through the lament, I is the urrent measured by 9. Repeat the measurements at dierent pressures. During eva uation the
the ammeter, and Rx is the lament resistan e. This formula is derived from air expands and its temperature together with the lament temperature
the fa t that R ≪ R1 + R3 and from the observation that in the balan ed de reases. If the pressure in reases both the air and the lament heat up.
bridge there is no urrent through the galvanometer so its ir uit bran h Therefore after eva uating the ylinder (or lling it with air) one should
an be onsidered as dis onne ted. wait for some time until the lament temperature stabilizes. This an be
dete ted by observing the readings of the bridge galvanometer. Only after a
LABORATORY ASSIGNMENT steady state is attained one an adjust the lament temperature.
When hanging the pressure one should arefully monitor the lament
1. Familiarize yourself with the ele tri al and va uum design of the installation.
temperature: when the pressure drops below one torr the amount of heat
2. Open the installation to atmosphere via the valve Va1 . Valves Va1 and Va2
transferred by the lament to air abruptly de reases and the lament an be
are losed by turning their handles lo kwise and opened by turning the
overheated. In this ase one should de rease the lament urrent, so that
handles ounter lo kwise.
overheating remains about 67 ◦ C.
3. Set r = 1 kOhm. Pressures ex eeding 10 torr are measured by the indi ator manometer, for
4. Turn on the power and measure the lament resistan e at room temperature less pressures one should use the U-shape oil manometer. The measurements
using the bridge. should be arried out at 810 points: 45 points in the operating range
5. Make sure that the urrent through the lament during measurements does of manometer M and 56 points in the operating range of the U-shape
not hange its temperature. To this end double r and measure the lament manometer.
resistan e. The result should be equal to the previous one. Oil manometer is handled as follows.
6. Reverse the dire tion of the urrent by the swit h K and measure the a) Eva uate the installation to ∼1·10−1 torr, whi h is a hieved by
lament resistan e again. If the result is dierent, the resistan e should ontinuous work of the va uum pump for ∼5 min with the valves Va2 , Va3
be al ulated as the arithmeti al mean of the results obtained for dierent opened and the valve Va1 losed.
dire tions. b) Close the valves Va2 and Va3 , turn o the pump, and open the valve
7. Cal ulate the lament resistan e at the temperature greater by ≈7 ◦ C than Va1 to ll the va uum pump with air at atmospheri pressure. After that
room temperature (the temperature oe ient equals 3.8 · 10−3 ◦ C−1 ). one should ll the installation with air to attain the dieren e of the U-
8. By adjusting r in rease the lament temperature by 67 ◦ C than room shape manometer levels of ∼0.5 m. This is done with the aid of the valve
temperature (at atmospheri pressure the urrent should be about 70 mA). Va2 whi h should be handled very arefully. One should slowly open the
Re ord the ammeter readings and measure the lament resistan e. Cal ulate valve while ontinuously monitoring the dieren e of the manometer levels.
the lament temperature (using its resistan e) and the dissipated Joule heat A sharp move of the valve handle let too mu h air pass in the installation
(a ording to its resistan e and the urrent). whi h kno ks the oil from one side of the manometer to the other.
The lament temperature an be in reased by two methods: ) A measurement (balan e the bridge, re ord the ammeter readings and
à) by in reasing the urrent through the lament using the resistan e r. the dieren e of the levels) should be repeated 23 times at the dieren e
In so doing one should maintain the bridge balan e by adjusting its ontrol of ∼0.5 m and ∼1.5 m. This is ne essary be ause some amount of air was
swit hes until the lament temperature rea hes the required range; sorbed (absorbed) by the oil at the atmospheri pressure in the installation.
á) by setting the al ulated value of the resistan e (the lament During eva uation of the installation to ∼0.1 torr this air is desorbed
temperature) using the bridge swit hes and then balan ing the bridge by (extra ted ba k) from the oil. The oil manometer is not inuen ed by the
adjusting the resistan e r. One should keep in mind that not only the desorption (sin e the air is released into both sides), whereas the thermal
lament temperature depends on the urrent but the bridge sensitivity as ondu tivity varies signi antly, whi h results in gradual unbalan ing of the
bridge. temperature jump an be ignored and Tr an be equated to the lament

d) To repeat the measurements at pressures ∼0.5 m and ∼1.5 m of the temperature.
oil olumn one should lose the valve Va1 , turn on the va uum pump, and Determine the lament temperature T using its resistan e and nd the
wait for ∼1 min while the tubing is eva uated to ∼0.1 torr, then open the temperature jump ∆T = T − T ′ . Plot ln T ∆T
−TR versus ln P .
Patm
valve Va2 (the valve Va3 must be losed). Cal ulate a temperature jump oe ient g from the formula whi h ould
If during this operation the right level of the oil manometer be omes be derived from Eqs. (2.12) (2.15):
lower than the left one (whi h means that air has been desorbed on the
right side), one should open the valve Va3 at operating pump, equate the ∆T R
g= r ln .
oil olumns on both sides and only then (i. e. ∼5 min later) lose the valves T ′ − TR r
Va3 and Va2 and repeat the operations of the item b). At pressures higher
than 1.5 m of oil olumn lling the installation with air and doing the Plot ln λg versus ln PP0 , where λ = λ0 PP0 and λ0 = 0.6 · 10−5 m is the mean
measurements an be arried out without the preliminary eva uation of the free path of air mole ule at standard onditions (the pressure of 760 torr
va uum pump. and the temperature of 0 ◦ C).
After ompleting the measurements with the oil U-shape manometer one Compare the results obtained with the previous al ulations of 1013.
should open the valve Va3 and do the measurements using the manometer 15. Estimate the length on whi h the temperature jump o urs. To do this use
M, by in reasing the pressure stepwise from ∼10 torr to the atmospheri Eq. (2):
pressure. One should set the resistan e of the de ade box to r = 1 kOhm ∆T A
at the atmospheri pressure and measure the lament resistan e at room ∆x ≈ = .
dT /dx P
temperature again. The reason is that during the measurements room
temperature and also the installation temperature ould hange. Sin e ∆T = Cal ulate ∆x for the three pressure values: 1 atm, 10 torr, and 0.5 torr.
= Tf − Tc is only ∼7 ◦ C, ∆T at the beginning of the measurements an be Compare the obtained values of ∆x with the mean free path at the
signi antly dierent from ∆T at the end of the measurements (Tf = const). orresponding pressure.
Think, how this an possibly ae t the data treatment. Compare the results with the value of g obtained in 14.
10. Plot the results in oordinates 1/P , (Tf − Tc )/Q (see Eq. (9)). Draw the
straight line through the points. Using the plot determine the numeri al Questions
values of the rst and se ond terms on the right hand side of Eq. (9). 1. Why does the heat transfer from the lament to the ambient air drop when the
pressure de reases from several torr to several de itorr?
11. Cal ulate the value of κ using the obtained values. How would the a ura y
of the result hange if the temperature jump were not taken into a ount? 2. Does the heat transfer depend on pressure at higher pressures? (Dis uss also the
me hanisms dierent from thermal ondu tivity.)
At what pressures an this orre tion be negle ted?
12. Find the value of B from the plot. Using it al ulate Af with the aid of Literature
Eq. (7). The term Ac /R an be negle ted ompared to Af /r. One an 1. Áåëîíó÷êèí Â.Å., Çàèêèí Ä.À., Öèïåíþê Þ.Ì. Îñíîâû èçèêè. Ò. 2. Êâàí
estimate the dis arded term by substituting Ac = Af . òîâàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 1, 1.3,
13. Cal ulate the temperature jump at all experimental values of pressure P 1.2.
using Eq. (8): ∆Tju = B(Q/P ). Plot ∆Tju versus P . 2. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976.
14. Cal ulate the temperature jump at all experimental values of pressure P ë. III, 45, 47.
dire tly from its denition (2.14) without an additional assumption made in 3. Sivuhin D.V. General ourse of physi s. V. II. Thermodynami s and mole ular
Eqs. (2) and (4) (9) that the jump is inversely proportional to pressure. To physi s. M.: S ien e, 1979, 89.
this end set TR = Troom in Eq. (1) and nd the extrapolated gas temperature 4. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001.
T ′ in the vi inity of lament assuming that T ′ = Tr . To do the al ulation Ñ. 7882.
determine experimentally the thermal ondu tivity oe ient (κ ), using the 5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1.
same formula (1) at the pressure about the atmospheri pressure when the Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 227231.
2.2.3. Measurement of thermal ondu tivity of
gases at atmospheri pressure
Rý
Purpose of the lab: to determine thermal ondu tivity of air or arbon
dioxide at atmospheri pressure and various temperatures by measuring
Rì
the heat transfer from the wire heated by ele tri urrent to ylinder
asing.
Tools and instruments: an installation for measurement of heat

transfer; a low va uum pump; a gasometer with arbon dioxide; a
manometer; a resistan e de ade box; a pre ision resistor of 10 Ohm; the
digital voltmeter Â7-38; and a sour e of ele tri urrent. 1
PSfrag repla ements 2

The basi fa ts about thermal ondu tivity of gases an be found in the
introdu tion to the previous lab. Solving Eq. (2.13) for κ one obtains:
Q 1 r2
κ= ln , (1)
T1 − T2 2πL r1
where r1 is the wire radius, r2 is the radius of the external ylinder and Fig. 1. Ele tri ir uit of setup for measuring thermal ondu tivity of gases
other notations are the same as in the lab 2.2.2.
The method of measurement of thermal ondu tivity used in the The experiment an be done with air or arbon dioxide (upon instru tor's
experiment is based on Eq. (1). hoi e) at atmospheri pressure. Before lling the tube it must be eva uated
and washed with the gas under study several times.
Laboratory setup. The installation is shown in Fig. 1. A thin ni kel or
The dependen e of the voltage a ross the wire on the urrent through it
wolfram wire is stret hed along the axis of a verti al opper tube1 The tube
is measured at a ertain temperature of the thermostat. The data are then
is lled by the studied gas via the valve. The wire is heated by ele tri
plotted in the oordinates of the dissipated power versus the wire resistan e.
urrent, its temperature T1 is determined by its resistan e. The tube is This dependen e is used to nd the wire resistan e at zero urrent, i.e. at the
en losed in a asing and its temperature is maintained onstant by the
thermostat temperature. The dire t measurement at low urrent is di ult
running water from a thermostat. The water temperature T2 is measured be ause of thermoele tri phenomena whi h signi antly distort the result.
by a thermometer lo ated in the thermostat. The heat transferred by the
Large urrent, on the other hand, raises the wire temperature. By repeating
gas (providing the losses through the tube ends an be negle ted) equals the
the measurement at various temperatures of the thermostat one an nd
Joule heat dissipated in the wire. The ele tri urrent through the wire is
the dependen e of wire resistan e on temperature. The oe ient of thermal
determined by the voltage a ross the pre ision resistor of 10 Ohm. Thus all
ondu tivity is then determined from the dependen e of the dissipated power
quantities on the right hand side of Eq. (1) an be dire tly measured.
on the temperature dieren e by means of Eq. (1). At small temperature
The ele tri ir uit of the installation in ludes the sour e of urrent, the dieren e the dependen e is well approximated by a straight line.
wire, the pre ision resistor of 10 Ohm, and the resistan e de ade box Rm
It should be noted that many fa tors an ae t the results of the
onne ted in series. The digital voltmeter an be onne ted either to the
experiment. Conve tion has been already mentioned. The heat transfer from
wire or to the pre ision resistan e whi h allows one to measure the voltage
the wire to the tube wall is partially due to radiation. Equation (1) does
a ross the wire and the urrent through it.
not take into a ount the heat losses through the wire ends. The detailed
1 The wire diameter is 2r ≈ 0.10 mm, the internal tube diameter is 2r ≈ 10 mm,
1 2
al ulation shows that they ontribute several per ent to the experimental
and the length L ≈ 400 mm. The exa t values an be found on the installation. error, whi h is the largest ontribution. To estimate the ee t one should
al ulate the heat transferred by the end of a ni kel wire several entimeters 6. Assuming that the temperature dependen e of the oe ient of thermal
in length by assuming that one end of the wire is kept at room temperature ondu tivity takes the form κ = AT β nd the exponent β . To do this plot
and the other end is at the temperature found from the data. ln κ versus ln T .
7. Estimate the experimental error.
LABORATORY ASSIGNMENT
1. Measure the dependen e of the voltage Uw a ross the wire on the voltage Questions
a ross the pre ision resistor Up . The interval of the re ommended urrents 1. A ording to kineti theory of gases the mean free path λ depends on on entration
n as λ = 1/(σn). What an you say about the temperature dependen e of σ using
depends on the wire material, the spe i values an be found on the
the results of 6?
installation. For ni kel wire the measurements should be done in the interval
2. Why does the installation for measurement of thermal ondu tivity of gas have
of 50150 mA (the orresponding Up , for instan e, is 0.5, 0.75, 1, 1.25, and the shape of a long thin verti al ylinder?
1.5 V). For wolfram wire the interval is 1070 mA. Be areful! Ex essive 3. Estimate the heat losses through the wire ends.
urrent an fuse the wire and damage the installation. 4. A thermal emf is usually several mi rovolts per kelvin. Estimate the urrent
After the urrent is hanged wait until a stationary regime is a hieved. through the wire for whi h a thermal emf in the voltmeter ir uit would
The readings should be re orded only if they do not vary with time. To signi antly ae t the results.
verify whether the stationary regime was a hieved it is re ommended to 5. What is the temperature dieren e between the wire and the tube at 150 mA?
return to the initial value Uw = 0.5 V and repeat it after the measurement Compare the result with the experimental value.
at Uw = 1.5 V. If the previous result is reprodu ed the thermal equilibrium 6. Equation (1) was derived under the assumption that the thermal ondu tivity is
was a hieved. independent of temperature, therefore the equation is valid if ∆T ≪ T . Assume
2. Repeat the measurements of 1 at several values of the installation temperature that the oe ient of thermal ondu tivity depends on temperature as κ ∼ T β
in the interval 2070 ◦ C. To do this noti e how mu h time the measurements and al ulate the exa t relation. Estimate the orresponding error of κ .
of 1 have taken and plan the experiment so that the last measurement Literature
was at 70 ◦ C. It is re ommended to do the measurements at three or four 1. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. II. Òåðìîäèíàìèêà è ìîëåêóëÿðíàÿ
temperature values, e.g. at 20, 40, 60 and 70 ◦ C. èçèêà. Ì.: Íàóêà, 1979. 52, 53, 89.
3. Plot the dependen e of the dissipated power Q = 0.1Uw Up [W℄ on the wire 2. Áåëîíó÷êèí Â.Å., Çàèêèí Ä.À., Öèïåíþê Þ.Ì. Îñíîâû èçèêè. Ò. 2. Êâàí
resistan e Rw = 10Uw /Up [Ohm℄. Using the plot determine the slope dQ/dR òîâàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 1, 1.3.
and the wire resistan e R0 at the thermostat temperature, i.e. at vanishing 3. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976.
dissipated power. ë. III, 45, 47.
4. Plot the wire resistan e R0 versus temperature. The points should t 4. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001.
a straight line. Cal ulate the slope dR/dT . It is also re ommended to Ñ. 7882.
determine the temperature oe ient of the wire material α = R273 5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1.
dT and
1 dR
ompare it with the tabulated value. Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 227231.
5. For every value of the installation temperature determine the oe ient of
thermal ondu tivity of the gas using the equations:
dQ 1 r2
κ= · ln ,
dT 2πL r1
dQ dQ dR
= .
dT dR dT
Plot the dependen e of the oe ient on temperature.
2.2.4. Measurement of thermal ondu tivity of Estimate of the heat losses. Equation (3) is obtained under the
solids assumption that the heat ow between the hot and the old walls remains
uniform. The assumption is justied if the plate thi kness is small ompared
Purpose of the lab: 1) to determine thermal ondu tivity of a solid by to its radius. However there is always a small but nite heat ow through
omparing it to the thermal ondu tivity of a standard; 2) to evaluate the
the lateral surfa e of the plates. The ow an be evaluated by measuring
relative heat loss through the lateral surfa e of a plate by measuring the
radial temperature distribution. the radial temperature distribution in the plates and the rate of temperature
de rease from the enter to the edge. Let us estimate quantitatively the heat
Tools and instruments: a thermostat; a set of thermo ouples; a mirror losses and nd its relative value.
galvanometer; sheet rubber gaskets; solid spe imens; an ebonite disk used The analysis of two-dimensional temperature distribution is based on the
as a standard; and a aliper. radial temperature dependen e obtained in the experiment, whi h allows one
to determine the density of radial heat ow qr . (This quantity is the radial
A ording to Eq. (2.7) the heat ∆q passing per se ond through a uniform omponent of ve tor q and a ording to Eq. (2.7) it is determined by the
partition of area S and thi kness ∆z is proportional to the temperature radial temperature gradient.) The total radial heat ow is the produ t of qr
dieren e ∆T and equals and the lateral area Sr :
∆T
∆q = κS , (1)
∆z ∂T
qr Sr = −κ2πrd . (4)
where κ is the thermal ondu tivity of the partition material. ∂r
The oe ient κ an be found from Eq. (1) providing ∆q , ∆T , ∆z , and Here d is the plate thi kness.
S are measured. However a measurement of the heat transfer is not an easy An axial heat ow is determined by the produ t of the temperature
task, whi h prevents an a urate determination of κ by this method. In this gradient along the symmetry axis z and the area of the ir le of radius r:
experiment κ is measured by an indire t method, namely, by omparing the
thermal ondu tivity of a studied material with that of a material whi h ∂T
qz Sz = −κπr2 .
oe ient κ is known pre isely. This allows one to avoid measuring ∆q . ∂z
Figure 1 illustrates the method.
The ratio of these ows is:
Two plates with dierent thermal ondu tivity oe ients κ1 and κ2
are rmly pressed between two walls whi h temperatures T1 and T2 are 2d ∂T
maintained onstant during the experiment. If the plates are thin enough, δ= ∂r
. (5)
r ∂T
i.e. d1 and d2 are small ompared to a transversal size of a plate, the heat ∂z
losses via their lateral surfa es are small as well. In this ase the heat transfer This parameter spe ies the widening of the heat ow and its relative
from the hot to the old wall is approximately onstant (an estimate is given losses, it is independent of the oe ient of thermal ondu tivity.
below). In this ase Noti e that δ is also independent of radius r, i.e. the ratio of radial and
axial ows is the same both on the symmetry axis and far from it. This an
∆T1 ∆T2
∆q = κ1 S = κ2 S . (2) be justied as follows. The radial temperature gradient in Eq. (5) is dire tly
∆z1 ∆z2 proportional to r, so this radius an els out the radius in the denominator.
Assuming that ∆z1 = d1 and ∆z2 = d2 one obtains: Besides, if the heat loss through the lateral surfa e is small the derivative
∂T /∂z in Eq. (5) an be taken as radius independent as well. Thus the
κ1 d1 ∆T2 widening of the axial heat ow is approximately onstant everywhere in a
= , (3)
κ2 d2 ∆T1 plate.
where ∆T1 and ∆T2 are the temperature dierentials on the plates. A Laboratory setup. The setup for measuring oe ient of thermal ondu tivity
thermal ondu tivity oe ient of a plate material an be determined if (see Fig. 1) onsists of a heater whi h temperature is T1 and a ooler T2 ; the
the other oe ient is known. temperatures are kept onstant. The heat ows from the heater to the ooler
Before measurements one should turn on the thermostat (move the

swit h to the upper position) and its heating-mixing unit (button ¾Pump¿)
To speed up heating the swit h ¾Heatinq Power adjustment¿ should be
shfted to the rightmost position. When water temperature approa hes 70 ◦ C
the swit h should be shifted to the leftmost position.
t1
By rotating the thermometer knob set a temperature higher than 70 ◦ C.
PSfrag repla ements When the temperature rea hes 70 ◦ C one should turn o the heater by
κ1 d1
slowly rotating the thermometer knob. The red indi ator will go out.
κ2 d2 If at the time of your oming the thermostat is already operating and
set to the desired temperature, start the experiment right away.
t2
LABORATORY ASSIGNMENT
Before measuring oe ients of thermal ondu tivity one should do
Fig. 1. Setup for measuring thermal ondu tivity oe ient by several preliminary experiments.
omparison method 1. Estimate experimentally the relaxation time onstant required for establishing
a stationary heat ow in the setup. To do this measure the temperature at
through the plates made of the studied material and the material used as any point as a fun tion of time, plot the results, and estimate the time
standard. onstant. Further measurements should be done after the stationary regime
An elasti material would be the most useful as the standard sin e it is established.
provides a reliable thermal onta t. Unfortunately, thermal ondu tivity Estimate the relaxation time onstant using Eq. (2.20). To do this
of many elasti materials, espe ially, rubber has a strong temperature determine the average value of the oe ient of thermal ondu tivity for the
dependen e in the range between 0 and 100 ◦ C, whi h prevents using plate assembly using the tabulated values (or use just one value). Compare
rubber as the standard. Instead ebonite is used in our setup. Its thermal the al ulated and the measured time onstants.
ondu tivity oe ient is 0.17 J/m·s·K. To provide the reliable thermal Noti e that one ould do the opposite, i.e. evaluate the average oe ient
onta t the plates are interlaid with thin rubber gaskets. The whole assembly of thermal ondu tivity using the experimental value of time onstant.
is pla ed under a s rew press. 2. Calibrate thermo ouples used in the experiment. To this end pla e the hot
The temperature T2 of the ooler is held onstant by running tap water jun tions of all thermo ouples at the same point of the setup (e.g. press them
(the tap is on the table behind the installation) and the temperature T1 of against the midpoint of the ebonite plate). Make sure that thermo ouple
the heater is maintained onstant by water from a thermostat. Temperature wires are parallel and do not tou h ea h other. Galvanometer readings are
is measured by means of four thermo ouples whi h hot jun tions are pla ed proportional to the sensitivity of a thermo ouple whi h an vary due to
at the enter of the plates. The old jun tions of two thermo ouples are dierent jun tion resistan es.1
pressed against both sides of the ebonite plate by rubber gaskets, the old If galvanometer readings a1 , a2 , a3 , and a4 are signi antly dierent, the
jun tions of two others are pressed against the studied plate. The se ond ratio in Eq. (3) should be al ulated as
thermo ouple jun tions are put into a ylinder lled with oil whi h is washed
by running tap water. In this setup the temperature of old jun tions is kept ∆T2
=
ϕ4 /a4 − ϕ3 /a3
, (6)
onstant during the experiment. ∆T1 ϕ2 /a2 − ϕ1 /a1
A mirror galvanometer an be onne ted to ea h thermo ouple with
the aid of a swit h. The galvanometer readings are proportional to the where ϕ1 , ϕ2 , ϕ3 , and ϕ4 are the galvanometer readings obtained in
temperature dieren e between the hot and old jun tions of a thermo ouple. the measurement of oe ient of thermal ondu tivity. The subs ripts
By measuring the temperature on both sides of a plate one an al ulate 1 Copper- onstantan thermo ouples used in the experiment are made by welding, so
the temperature dierential. their sensitivity does not dier mu h.
orrespond to thermo ouples. Quantities ai and ϕi should be measured with along the symmetry axis.
the galvanometer onne ted to the same thermo ouple. Use the values obtained for al ulation of the relative heat losses
Derivation of Eq. (6) is suggested as an exer ise. It should be noted that a ording to Eq. (5).
absolute sensitivity of thermo ouples are not relevant in the dimensionless Questions
ratio ∆T
∆T1 , the relative sensitivity will do.
2
1. What is the denition of the oe ient of thermal ondu tivity and what is its
3. Verify the assumption of temperature independen e of the oe ient of dimension?
thermal ondu tivity of the standard plate. To do this prepare a setup 2. Derive an equation similar to Eq. (3) whi h takes into a ount a hange in the
of two identi al ebonite plates interlaid with rubber gaskets. Measure the heat ow area, say, from S1 to S2 .
temperature dierentials on the ebonite plates with the aid of thermo ouples. 3. Derive Eq. (6) whi h takes into a ount a dieren e in thermo ouple sensitivity.
The plates have dierent temperatures. If their thermal ondu tivity 4. Can the dependen e of thermal ondu tivity oe ient of ebonite be measured
oe ient is temperature independent, a dierential must be proportional using this parti ular installation? Are the heat losses through the lateral surfa e
to the plate thi kness, as it follows from Eq. (3). Measure the thi kness using signi ant enough to prevent the measurement?
a aliper. 5. Using the experimental points of the radial temperature dependen e plot isotherms
and sket h the lines of heat ow. (It should be at least three isotherms and ow
4. Measure oe ients of thermal ondu tivity of the spe imens (plexiglas, lines whi h span the whole plate area.)
CEM, and FR-2). Using the galvanometer readings and thermo ouple
sensitivity determine the temperature dierential at the spe imen and Literature
1. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. II. Ì.: Íàóêà, 1975. 5254, 57.
ebonite plates for ea h spe imen a ording to Eq. (6), then use Eq. (3).
It is re ommended to do measurements twi e for ea h spe imen: by
pla ing the spe imen next to the ooler and then next to the heater. By 3. Ëàíäàó Ë.Ä., Àõèåçåð À.È., Ëèøèö Å.Ì. Êóðñ îáùåé èçèêè. Ì.: Íàóêà,
omparing the results one an estimate the temperature dependen e of the 1965. 109, 110.
oe ient providing it ex eeds the orresponding dependen e of the ebonite 4. Êóðñ èçèêè / Ïîä ðåä. Í.Ä. Ïàïàëåêñè. Ò.1. Ì.-Ë.: îñòåõèçäàò, 1948.
measured in the experiment with two ebonite plates. ë. XIV.
5. The heat losses through the lateral surfa e of the assembly an be evaluated
as follows. Pla e the hot jun tions of thermo ouples at various distan es
from the enter, i.e. at 0, 1, 2, 3 m, or pla e one at the enter, another 2.2.5. Determination of vis osity of liquid by its
one at the edge, and two jun tions in-between. Re ord the distan es, they outow through apillary
will be ne essary in data treatment. To minimize the error aused by heat
transfer through the thermo ouple wires, their segments pressed between Purpose of the lab: 1) to determine water vis osity by measuring a
the layers must have equal length. Using the galvanometer measure the volumetri rate of its ow through a apillary; 2) to determine vis osity
jun tion temperatures and plot the temperature (galvanometer readings of another liquid by omparing its ow rate with that of water.
divided by thermo ouple sensitivity) versus radius. A temperature de rease Tools and instruments: a Mariotte's bottle; a apillary; a graduated
away from the enter is due to the heat ow through the lateral surfa e. ylinder; a stopwat h; a glass; and a mi ros ope on a support.
Using the plot evaluate the radial derivative of the temperature (in the
units of galvanometer readings divided by sensitivity). Consider a stationary laminar ow of a uid through a ir ular apillary
It is re ommended to determine the derivative somewhere lose to the (see Fig. 1). In this ow onsider a ylinder of radius r and length l. Let
edge, the measurements there are more a urate. Or one an interpolate the pressure at the ylinder ends be P1 and P2 . In a stationary ow the net
and even extrapolate the plotted urve to the plate radius. Noti e that if for e a ting on the ylinder due to pressure, (P1 − P2 )πr2 , is balan ed by
the radial temperature distribution is lose to parabola, the derivative at the fri tion exerted on the ylinder lateral side by the adja ent layers of the
any point is two times greater than the slope of the urve onne ting the uid. The tangential stress in a uid a ording to Eq. (2.6) is
temperature at this point to the temperature in the enter. dv
Find the axial derivative of the temperature by pla ing the hot jun tions τ = −η . (1)
dr
The net fri tion is is smaller than the latter the turbulent os illations are damped by vis osity
dv and the ow remains laminar. The ratio of kineti energy of a uid element
Ff r = Sη ,
dr ρv 2 L to the work done by vis ous for e at the hara teristi length η Lv L2 · L
where S is the ylinder surfa e area, η is vis osity, and dv/dr is the velo ity determines the dimensionless Reynolds number:
gradient. Substituting 2πrl for S and equating the net for e exerted on the
vRρ
ylinder to zero, one nds: Re = , (4)
η
dv
(P1 − P2 )πr2 + 2πrlη = 0. where v is the typi al ow velo ity, e.g. for a ow in a pipe it is the velo ity
dr
averaged over the ow rate, R is the typi al ow size (the pipe radius), ρ is
Integrating this equation one obtains: a uid density, and η is a vis osity oe ient (1). Let us write Eq. (4) as
P1 l P2 P1 − P2 2 2
v=− r + C, 2 ρv2
4ηl Re = v . (5)
epla ements ηR
R where C is a onstant of integration whi h In this form the Reynolds number an be understood as the doubled ratio
r must be found from boundary onditions. of kineti energy of a uid element ρv 2 /2 to the typi al uid stress due to
To determine it noti e that the uid velo ity fri tion ηv/R.
vanishes at r = R, in other words the uid A ording to Bernouilli's equation the kineti energy of in ompressible
¾sti ks¿ to the wall. Therefore: uid at small velo ity,
Fig. 1. To derivation of the P1 − P2 2 ρv 2
Hagen-Poiseuille law v= (R − r2 ). (2) = P0 − P,
4ηl 2
is equal to the dieren e between the pressure P0 in the region where the ow
Thus the uid velo ity varies as the velo ity vanishes and the pressure P in the region where the ow velo ity is
square of radius and it is maximal at the ylinder axis (at r = 0). v . Thus, kineti energy of uid an also be dened as dynami pressure.
The volumetri ow rate Q, i.e. the volume passing the ylinder ross- The hara teristi vis ous stress ηv/R an be obtained from Eq. (1), τ =
se tion per se ond is = −ηdv/dr, by estimating the derivative as the ratio of the hara teristi
velo ity v to the hara teristi size R (the pipe radius).
ZR
V P1 − P2 4 In a smooth ir ular pipe the transition from laminar to turbulent ow
Q= = v · 2πr dr = π R . (3) o urs at Re ≈ 1000.
t 8ηl
0 One should verify that a ow is laminar before using the Hagen-Poiseuille
equation in al ulations.
Equation (3) is alled the Hagen-Poiseuille law. Therefore uid vis osity an
be found by measuring the ow rate Q, the pressure dieren e P1 − P2 , the When a ow passes from a wide tube to apillary there is a transition
region of length a before laminar ow is formed,
pipe length l, and its radius R.
Slow uid motion an be understood as a motion of dierent layers with a ≈ 0.2R · Re. (6)
various onstant velo ities. Su h a motion is alled laminar. As the ow
velo ity grows the uid motion be omes in reasingly ompli ated, the layers Equation (3) an be trusted only if the apillary length is mu h greater than
mix, and the ow turns into turbulent. In this regime the ow velo ity at any a.
point rapidly hanges its magnitude and dire tion, only the average velo ity
is onserved. À. Measurement of water vis osity
A parti ular regime of a uid ow depends on the relation between kineti The installation for measuring vis osity of water is shown in Fig. 2. Water
energy of the uid and the work done by vis ous for e. If the former quantity ows out from a Mariotte's bottle through a alibrated apillary atta hed to
the bottle side near the bottom. The Mariotte's bottle maintains onstant
pressure dieren e P1 − P2 a ross the apillary ends although the water
level de reases in the pro ess. This is a hieved due to the tube B that passes
through the ork plugging the bottle and whi h is open to atmosphere.
When water ows out of the bottle the pressure in the upper part of
the bottle is less than atmospheri pressure by the pressure of the water
olumn between the upper water level and the lower end of the tube B. At
the same time there is no water in the tube. As water is owing out its level B
de reases and the pressure in the upper part of the bottle de reases as well. Ì
The pressure at the lower end of the tube B be omes less than atmospheri
pressure, i.e less than the pressure of air inside the tube. Be ause of the h A
pressure dieren e the water surfa e at the tube end bends downward and PSfrag repla ements
C
after a riti al pressure dieren e is a hieved an air bubble leaves the tube,
as ends to the upper part of the bottle, and in reases the pressure there.
This pro ess keeps going during the outow, so barring the minor pulses the
same pressure dieren e is maintained. Ï
To summarize: the pressure dieren e is determined by the height h of
water olumn between the axis of apillary A and the lower end of the
verti al tube B. The height is measured by mi ros ope M atta hed to a
Fig. 2. Installation for measuring water vis osity
plunger piston whi h an move in verti al dire tion. A plunger position an
be a urately determined using a vernier s ale.
The volume of owing out water is measured with graduated ylinder Ï. 3. Measure time interval ∆t required to ll the ylinder to a 2025 ñì3 mark.
The time is measured by a stopwat h. The apillary length is measured with Repeat the measurement and verify that ∆t is independent of the water
a ruler and the apillary diameter is measured by means of omparator ÈÇÀ- level in the bottle but it is determined by the depth of immersion of the
2 or mi ros ope ÌÈ. The apillary diameter must be measured as tube B. Close the apillary with the plug C.
a urately as possible: the diameter is raised to the forth power in Eq. (3), 4. Using the mi ros ope on a verti al support measure the distan e h (see
so it's error ontributes the most to the total error. Fig. 2) between the axis of horizontal apillary and the lower end of the
tube B. The pressure dieren e ∆P = P1 − P2 a ross the apillary is not
LABORATORY ASSIGNMENT exa tly equal to h (in the appropriate units) but in ludes a orre tion ∆h due
1. Measure the internal diameter of the apillary. One should not attemp to
to surfa e tension. The orre tion an be measured as follows. By gradually
remove the apillary from the Mariotte's bottle: there is a separate pie e of
lowering the tube B nd the height ∆h at whi h water stops owing out of
the same apillary in a spe ial holder. Install it verti ally into the spe ial
the apillary. This means that the pressure of the water olumn ∆h between
slit of the table of omparator ÈÇÀ-2 or use the mi ros ope ÌÈ. Measure
the apillary axis and the lower end of the tube is balan ed by surfa e tension
the apillary diameter several times using dierent diameters and average
of the air bubble at the end of tube B and the water bubble at the end of
the results.
tube C.
Measure the apillary length with the ruler.
2. Plug the apillary with rubber plug C. Fill the bottle with distilled water 5. Raise the tube B so that the height h is 23 times greater than ∆h and
and plug the bottle using the ork with tube B. Remove the plug C, the measure the interval ∆t required to ll the ylinder with V = 2025 ñì3 of
water starts owing out to the graduated ylinder. Wait until water bubble water. Measure the height h. Then ∆P = P1 − P2 = (h − ∆h)ρg .
formation starts on the lower end of the tube B. At this moment the Measure the volumetri ow rate for 45 values of h up to the maximum.
stationary pressure distribution is a hieved and one an begin measurement 6. Using Eq. (4) verify that ea h time the ow in the apillary is laminar. Using
of the volumetri ow rate. Eq. (6) estimate the length a of the transition region. To estimate Re and a
assume that water vis osity η ≈ 0.01 P (poise). A quantitative des ription of the ow through the apillary is based on
7. Plot the results in oordinates h, Q. Equation (3) shows that for laminar Eq. (3). The pressure dieren e P1 − P2 in Ostwald vis ometer depends on
ow h is dire tly proportional to Q. In a regime deviating from the laminar the level of liquid in the bulb and varies during the measurement. Therefore
the pressure dieren e grows faster than the ow rate. Therefore only the Eq. (3) ould be applied only to short time intervals. In so doing the volume
straight part of the urve an be used to extra t η . Vis osity is found from of the liquid Qv passing through the apillary per se ond should be repla ed
the slope of this part. Noti e that using this method it is not ne essary to by −dV /dt, where V is the volume of liquid in the bulb B1 . The pressure
know the height ∆h (∆h is the inter ept Q(h) on the axis h at Q = 0). dieren e P1 − P2 equals ρh(V )g where ρ is the liquid density and h is the
Determine the water vis osity and estimate the error. Compare the value of height of its olumn. This height is a fun tion of the liquid volume in the
∆h found from the plot with the value measured in 4. bulb, h(V ), whi h is spe ied by the vis ometer geometry and is not relevant
for our purposes. It is important that h(V ) is independent of a parti ular
liquid.
Á. Measurement of vis osity of water-gly erol solution It follows from the above argument that Eq. (3) should be written as
using Ostwald vis ometer.
dV πR4 h(V )ρg 8l dV ρg
In the rst part of the experiment water − = , or − = dt.
dt 8l η πR4 h(V ) η
vis osity is determined dire tly, i.e. by measuring
T D the apillary dimensions and the volumetri ow Let us integrate this equation between initial and nal values, V = V0 , t = 0
rate. A omparison method is more ommon, in and V = V1 , t = t1 :
0 whi h vis osity of a studied liquid is ompared Z1
V tZ1
B1 to the known vis osity η0 of another liquid. The 8l dV ρg
4
=− dt.
1 measurement is done by means of a simple devi e πR h(V ) η
V0 t0
alled Ostwald vis ometer whi h is shown in Fig. 3.
The measurement onsists in omparing the time Now noti e that the expression on the left is some onstant whi h is
epla ements C taken by the same volume of studied liquid and determined by the vis ometer geometry and the initial and nal levels of the
the liquid with known η0 to pass through the same liquid. Thus the results of measurements with dierent liquids are related
apillary. In the se ond part of the experiment one as:
ρ1 ρ2 ρ3
B2 determines vis osity of a water-gly erol solution at t1 = t2 = t3 = . . . (7)
η1 η2 η3
room temperature using Ostwald vis ometer.
Ostwald vis ometer (see Fig. 3) is a glass U-tube. Doing the measurement rst with water (subs ript 0) and then with
One side of the tube has a bulb B1 with marks ¾0¿ another liquid (subs ript x) one nds:
and ¾1¿ and a apillary C. The other side is a wide ρ x tx
Fig. 3. Ostwald tube D with a bulb B2 . ηx = η0 . (8)
ρ 0 t0
vis ometer The wider vis ometer tube is lled with water
whi h vis osity η0 is known. Using a rubber dou he This is the nal formula.
atta hed to the tube T water is su ked to the tube so that its level is above In the experiment one measures vis osity of 10-, 20-, 30-per ent gly erine
the mark ¾0¿. Removing the dou he and holding the vis ometer verti ally solution at room temperature. The vis osity of distilled water at room
one allows water to ow freely through the apillary C. When the level temperature should be taken from the rst part of the experiment, where it
passes the mark ¾0¿ one starts a stopwat h and stops it when the water was dire tly measured.
level passes the mark ¾1¿. Thus one measures the time t0 taken by the
volume V between the marks in the bulb B1 to pass through the apillary. LABORATORY ASSIGNMENT
The apillary diameter and the pressure dieren e in Ostwald vis ometer 1. Wash the vis ometer using distilled water. To do this pour enough water
is hosen so that liquid ow in the apillary is always laminar. into the wide tube D of vis ometer (see Fig. 3) to ll the bulb B2 . Using
the rubber dou he onne ted to the narrow tube T raise water so that to 2.2.6. Determination of a tivation energy of
ll the bulb B1 and then allow it to ow freely through the apillary. Pour liquid via temperature dependen e of its vis osity.
the water out. Repeat the pro edure twi e.
2. Measure the time taken by water to pass between the marks ¾0¿ and ¾1¿. Purpose of the lab: 1) to measure velo ity of spheres falling in liquid
To this end pour 5 m3 of distilled water into the vis ometer. Repeat the at various temperatures; 2) to determine vis osity of liquid using Stokes'
law and to evaluate a tivation energy.
measurement 45 times and average the results. Liquid vis osity signi antly
depends on temperature. To stabilize it immerse the vis ometer into a glass
Tools and instruments: a glass ylinder lled with gly erol; a
of water at room temperature during the experiment. thermostat; a stopwat h; an opti al omparator; a mi ros ope; and small
3. Empty the vis ometer and pour 5 m3 of 10-per ent gly erine-water solution spheres about 1 mm in diameter.
into it. Measure the time of passing through the apillary. Repeat the
experiment 45 times. Do the same experiment with 20- and 30-per ent Liquids are similar both to gases and solids. Similar to gas, a liquid
solutions. a epts the shape of a ontainer whi h it lls. Similar to solid, a liquid is
4. Determine the density of the studied solutions using a s ale. dense and di ult to ompress.
5. Cal ulate vis osities of the studied solutions using Eq. (8). Estimate the This two-fold nature of liquids is related to motion of their mole ules.
error of the result. Mole ules of gases move randomly, their arrangement is disordered. The
parti les in rystals os illate near ertain equilibrium positions, the sites of
rystal latti e. In liquids the mole ules reside in potential wells of ele tri
Questions eld reated by nearby mole ules, like in rystals. The mole ules os illate
1. Why is it re ommended to determine the vis osity of water by a graphi al method
with a frequen y lose to the os illation frequen y in rystals (∼1012 Hz),
in the rst experiment? Wouldn't be better to determine the vis osity dire tly for
dierent tube heights? It seems that averaging the results one ould a urately
and with the amplitude determined by the available volume. The depth
nd the vis osity and estimate reliably the experimental error by the dispersion of the potential well in liquids is greater than the average kineti energy
of results. What is wrong with this approa h? of os illation, so the mole ules os illate around almost stable equilibrium
2. The pressure dieren e that must be applied to for e a liquid through a pipe at a positions. However the dieren e between the potential and kineti energies
given velo ity (assuming laminar ow) depends on liquid vis osity. Does vis osity is not large, so a mole ule often leaps out of ¾its¿ potential well and o upies
matter if the ow is turbulent? What parameters of the liquid are required in this the nearby one.
ase? Unlike solids liquids have ¾porous¿ stru ture. It has va ant sites, ¾holes¿,
whi h allow a mole ule to move from its pla e to a nearby hole. In so
Literature doing the mole ules slowly move around and mostly reside near equilibrium
1. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. I. Ìåõàíèêà. Ì.: Íàóêà, 1979. ë. VII, positions, so the whole stru ture resembles a latti e gradually hanging with
97, 98. time. It is usually said that liquids are hara terized by a short-range order:
2. Êèíãñåï À.Ñ., Ëîêøèí .., Îëüõîâ Î.À. Îñíîâû èçèêè. Ò. 1. Ìåõàíèêà, the arrangement of mole ules is ordered in small volumes but the order
ýëåêòðè÷åñòâî è ìàãíåòèçì, êîëåáàíèÿ è âîëíû, âîëíîâàÿ îïòèêà. Ì.: Ôèç disappears with distan e.
ìàòëèò, 2001. ×. 1. ë. 8, 8.38.6. It has already been mentioned that a mole ule must over ome the
3. Ïîëü .Â. Ìåõàíèêà, àêóñòèêà è ó÷åíèå î òåïëîòå. Ì.: îñòåõèçäàò, 1957, potential barrier whi h ex eeds the average thermal kineti energy in order
8790. to leave an equilibrium position. This happens when the kineti energy
4. Ëàíäàó Ë.Ä., Àõèåçåð À.Â., Ëèøèö Å.Ì. Ìåõàíèêà è ìîëåêóëÿðíàÿ èçèêà. in reases due to thermal u tuation by the quantity W alled a tivation
Ì.: Íàóêà, 1969. 119. energy. The larger the a tivation energy, the more seldom are the transitions
5. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001. between the positions of equilibrium.
Ñ. 8385. This model explains slow diusion and relatively large vis osity of liquids
6. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1. ( ompared to gases). Vis osity in gases an be attributed to momentum
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 155157. transfer by mole ules during their thermal motion. In liquids this pro ess is
omparatively slow. The number of mole ules with the energy greater than ow velo ity (or rather at large Re) the resistan e for e is proportional to
W is proportional to the Boltzmann fa tor. The temperature dependen e of the velo ity squared while for small velo ities (small Re) the for e is dire tly
vis osity is given by Eq. (2.17): proportional to the velo ity. Thus for small velo ity α = 1. Equating the
powers of mass, length, and time on both sides of the equation we obtain:
η ∼ AeW/kT . (1) 1 = x + z , 1 = −x + 1 + y − 3z , and −2 = −x − 1, when e x = 1, y = 1, and
z = 0. Therefore
This equation implies that vis osity of a liquid must rapidly de rease with F = Aηrv.
in reasing temperature. A ording to Eq. (1) the plot of vis osity logarithm
ln η versus 1/T must be a straight line whi h slope determines the a tivation The dimensionless fa tor A an not be found from the dimensional analysis
energy W . Experiment shows that Eq. (1) agrees with data in a moderate alone; the exa t solution gives the value 6π .
temperature range. For a larger temperature range the agreement is poor; In our derivation of Stokes' law we assumed that the velo ity is
this is not surprising sin e the equation is derived under rather rude ¾su iently small¿ without spe ifying any riterion of the ¾smallness¿. In
assumptions. fa t, the appli ability of Stokes' law must be justied by experiment. If the
In our experiment the temperature dependen e of liquid vis osity is law applies it an be used to determine the vis osity of the liquid.
determined by Stokes' method whi h is based on measurement of the velo ity
of a sphere freely falling in the liquid. The method is based on the following Consider the free fall of a sphere in vis ous liquid. There are three for es
assumptions. exerted on the sphere: the gravity for e, the buoyan y for e, and the vis ous
Any obje t moving through a vis ous uid experien es a resisting for e. for e whi h depends on the sphere velo ity.
In general the for e depends on many fa tors: the uid vis osity, the obje t Let us derive the equation of motion of the sphere. A ording to Newton's
shape, the type of the ow around the obje t, and so on. Stokes exa tly se ond law:
solved the problem of laminar ow around a sphere in vis ous uid. In this dv
ase the drag for e F is determined by the equation V g (ρ − ρl ) − 6πηrv = V ρ , (3)
dt
F = 6πηrv, (2) where V is the sphere volume, ρ is the sphere density, ρl is the liquid
density, and g is the gravitational a eleration. Solving this equation for v
where η is the liquid vis osity, v is the sphere velo ity, and r is its radius. one obtains:
The derivation of Stokes' law is ompli ated. Here we obtain an v(t) = vt − [vt − v(0)]e−t/τ . (4)
approximate solution using dimensional analysis. To do so we rst have to
Here v(0) is the initial sphere velo ity and
gure out the parameters whi h determine the resistan e for e of the uid.
Obviously, in our ase they are η , v , r, and the uid density ρl . The for e is V g (ρ − ρl ) 2 (ρ − ρl ) Vρ 2 r2 ρ
sought as a power dependen e: vt = = g r2 , τ= = . (5)
6πηr 9 η 6πηr 9 η
F = Aη x ry ρzl v α ,
Equation (4) shows that the sphere velo ity tends to the terminal velo ity
where A is a dimensionless fa tor and α, x, y , and z are the exponents to vt a ording to exponential law. The exponent is determined by the quantity
be determined. They an be found by equating the dimensions of the left- τ alled time of relaxation. If the time of the fall is several times greater than
and right-hand sides of the equation1 . Sin e the dimension of any quantity the time of relaxation, the velo ity an be onsidered as terminal during the
is determined by the powers of length, time, and mass, we obtain three fall.
equations for four unknowns α, x, y , and z . One an see that the posed By measuring the terminal velo ity vt and the quantities r, ρ, and ρl one
problem does not have the unique solution. Experiment shows that at large an determine the liquid vis osity from Eq. (5):
1 The dimension of vis osity an be easily found from Newton's equation F = ηS dv/dl; 2 2 ρ − ρl
it is equal to [M L−1 T −1 ]. η= gr . (6)
9 vt
and 2, respe tively. The notations on both gures are the same.
The ontainer is made of stainless steel en losed in a asing.
The thermostat ontrol unit in ludes a water pump whi h provides water
ir ulation, a heater, a temperature gauge, a water level gauge, ontrols, and
indi ators.
Turning on the thermostat. Turn the temperature ontrol knob 4 to
the outmost left. Turn on the power swit h 8. This will highlight the power
swit h, start the mixer, and turn on the digital temperature indi ator and
green indi ators 6 of the water level and the heater 7.
If at the start or during thermostat operation the red indi ator 6 of the
water level lights up, one should rell the water.
Set the ne essary operation temperature (∼15 ◦ C). To this end do the
following: push the button 5 to swit h the thermostat into the temperature
setting mode; the temperature being set is indi ated. Using the knob 4
hoose the required value.
Pushing the button 5 again will display the urrent temperature on
the indi ator. If it is higher than required, it is ne essary to run the
tap water through the ooling ir uit. This would ool the water in the
thermostat to the required temperature. For subsequent temperature values,
the thermostat will heat the water. The heater operation is indi ated by the
Fig. 1. Installation for measuring vis osity of liquid red indi ator. When the water temperature approa hes the required value,
the heater turns o temporarily, whi h is indi ated by the green indi ator.
Laboratory setup. The experimental installation in ludes the glass ylinder The measurement of terminal velo ity of the falling spheres should be
B lled with gly erol. The diameter of the ylinder is ≈3 m, the length is done no sooner than thermal equilibrium of the system is attained.
≈40 m (the exa t size is shown on the installation). There are two horizontal Several measurements with spheres of various diameters should be
marks on the ylinder wall at some distan e apart. The upper mark must performed at ea h value of the temperature. The gly erol density at ea h
be lo ated below the gly erol level, so that a sphere passing the mark had temperature is determined from the diagram in Fig. 3. The data obtained
the terminal velo ity. By measuring the distan e between the marks with a is then used to plot the graph in the oordinates ln η and 1/T .
ruler and the time of the fall with a stopwat h one determines the terminal
velo ity vl of a sphere. The ylinder B is pla ed in a asing D, through whi h
Comments. The method of determination of vis osity des ribed above is
based on Stokes' law, so the method is justied if the assumptions made
water from a thermostat is running. The water temperature in the asing D
in derivation of the law are fullled. The most reliable method of verifying
equals the gly erol 12 temperature when the thermostat is operating.
the assumptions is the following. The spheres of dierent radii have dierent
The radius of a sphere is measured with the aid of an opti al omparator terminal velo ities and dierent relaxation times. If the values of η al ulated
or a mi ros ope. The parti les are not ideally spheri al, so it is re ommended from Eq. (6) are the same for dierent spheres used in the experiment, one
to measure the sphere diameter several times and al ulate the mean value. an on lude that Eq. (2) orre tly des ribes the dependen e of vis ous for e
The sphere density ρ is tabulated (ρsteel = 7.7 g/ m3 , ρglass = 2.6 g/ m3 ). on sphere radius. Independen e of η on r serves as an indi ator of the validity
The gly erol density ρl (T ) is determined from the diagram in Fig. 3. of the theory and the experiment.
The experiment is done at several temperatures in the range from room Treatment of the experimental results is justied only if the values of
temperature to 5060 ◦ C. η do not exhibit a systemati dependen e on r. If su h a dependen e is
The installation design and the thermostat photo are shown in Figs. 1 revealed, it is mostly due to the inuen e of the ylinder walls. In this ase
7
glyc , g/cm3
8
6
1
5
3
9
4
2
10 Fig. 3. Gly erol density versus temperature
11
one should use a more pre ise formula instead of Eq. (6):
2 2 ρ − ρl
η= gr , (7)
9 [1 + 2.4(r/R)]vt
where R is the ylinder radius. For small spheres the dieren e between
Eqs. (7) and (6) lies within the experimental error and an be negle ted.
(Equation (7) is derived for spheres falling along the ylinder axis provided
r ≪ R.)
It is useful to study the limits of appli ability of Stokes' law from the
theoreti al viewpoint. Stokes' law is derived under the assumption that
the ow around the sphere is laminar. It is well known that the type of
ow is determined by the value of the Reynolds number, Re = vrρl /η . A
Fig. 2. Thermostat
ow an be onsidered laminar only at small values of Re (less than 0.5).
1 thermostat ontrol unit; It is re ommended to al ulate the Reynolds numbers for various radii of
2 ontainer; the spheres and at dierent temperatures. It is also useful to evaluate the
3 display; relaxation time τ and the path S whi h an be found by integrating Eq. (4).
4 temperature ontrol knob; Assuming for simpli ity that v(0) = 0 (whi h is usually valid with su ient
5 swit h between temperature setting/ ontrol modes; a ura y) one obtains:
6 indi ator of water level;
7 heater indi ator; t
8 power swit h; S = vt τ − 1 + e−t/τ . (8)
τ
9 lid;
10 inlet and outlet of the pump; One an easily see from Eq. (8) that S ≫ τ vt for t ≫ τ .
11 inlet and outlet for running water (to plumbing) The last inequality sets the limit on the allowed distan e between the
gly erol level and the upper mark.
LABORATORY ASSIGNMENT 2.2.7. Experimental study of gas diusion

1. Sele t 1520 spheres of various size and measure their average diameters through porous medium
using the omparator or mi ros ope.
2. Measure the terminal velo ities of the spheres and al ulate vis osity η using Purpose of the lab: 1) to measure the time dependen e of helium
Eq. (6). The measurements must be performed at 45 temperature values in on entration in air at various initial pressures of a gas mixture; 2) to
measure the oe ient of gas diusion through a porous medium; 3) to
the range between room temperature and 5060 ◦ C. For ea h temperature
determine the geometri hara teristi s of the porous medium using the
determine the density ρl using the plot ρl (T ) in Fig. 3. dependen e of diusion oe ient on pressure.
3. For ea h experiment al ulate the Reynolds number Re, the relaxation time
τ (using Eq. (5)), and the relaxation path S = vt τ . Verify appli ability of Tools and instruments: an experimental installation; a stopwat h;
Stokes' law for ea h experiment. voltage sour es (3 V, 12 V, and 220 V); an ammeter; and a resistan e
4. Plot the dependen e of ln η on 1/T . de ade box.
5. Determine the a tivation energy using Eq. (2.18) and the slope of ln η(1/T ).
Cavities in a porous medium usually form a ompli ated system of
6. Estimate the experimental error.
hannels. For example, this takes pla e in powders, sand layers, and many
Questions other arti ial materials. The observation and study of gas diusion in su h
1. The model of liquid onsidered in this lab implies that moving a mole ule to a media is of parti ular interest.
neighboring ¾hole¿ requires disrupting its bonds with the neighboring mole ules. Let us onsider the theory of gas diusion through a porous material. For
The bond disruption also o urs during evaporation of the liquid, so one ould simpli ity we assume that all avities in the material form a set of hannels
expe t that the a tivation energy would be lose to the vaporization heat per going through the bulk in various dire tions. We introdu e the following
mole ule. Does the experiment verify this on lusion? Take the tabulated value notations:
for the vaporization heat. d is the ee tive hannel diameter;
2. Steel spheres of dierent diameters are used in the measurement of liquid vis osity δ is the porosity oe ient whi h equals the ratio of the volume of the
by Stokes' method. Whi h spheres, small or large, are better suited for the avities to the net volume of the material;
experiment? ξ is the tortuosity oe ient whi h equals the ratio of the width of a
Literature porous layer to the average length of the path traveled by a mole ule during
1. Êèíãñåï À.Ñ., Ëîêøèí .., Îëüõîâ Î.À. Îñíîâû èçèêè. Ò. 1. Ìåõàíèêà, its diusion through the layer.
ýëåêòðè÷åñòâî è ìàãíåòèçì, êîëåáàíèÿ è âîëíû, âîëíîâàÿ îïòèêà. Ì.: Ôèç It is easy to see that δ and ξ are dimensionless and their value lies between
ìàòëèò, 2001. ×. 1. ë. 8, 8.38.6. zero and unity.
2. Ôðèø Ñ.Ý, Òèìîðåâà À.Â. Êóðñ îáùåé èçèêè. Ò. I. Ôèçè÷åñêèå îñíîâû ìå We shall study the simplest example of diusion: the diusion in a two-
õàíèêè. Ìîëåêóëÿðíàÿ èçèêà. Êîëåáàíèÿ è âîëíû. Ì.: Ôèçìàòãèç, 1962. omponent gas mixture in whi h the on entration of one of the omponents
ë. IX, 78, 95. is small. In this ase the problem is simplied, and the study of mutual
3. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001. diusion is redu ed to the study of the diusion of the minority substan e.
Ñ. 5557. The pro ess of diusion is des ribed by Fi k's rst law (2.5). In one-
4. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1. dimensional ase (the on entration depends on x- oordinate but not on
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 215. y and z ) and far from the walls the equation reads:
dc
j = −D , (1)
dx
where c is the on entration of a omponent (the number of parti les per
unit volume), j is the diusion ux of the omponent along the x-axis (the
number of mole ules rossing a unit area perpendi ular to the x-axis per
se ond), and D is the diusion oe ient. The minus sign in Fi k's rst law i.e. X
means that the substan e moves from a region of higher on entration to a Si = δ ξS, (6)
region of lower on entration; and the more the on entration gradient (the i
value of dc/dx) is, the higher is the diusion ux. The diusion oe ient D
where S is the ross-se tional area of the porous body. Using these
depends on gas omposition and its pressure; the theoreti al estimate (2.5)
expressions and substituting hDi i with D1 we nd
leads to the following equation:
1 dc
D= vλ. (2) Itot = −δ ξ 2 D1 S. (7)
3 dx
Here v is the mean thermal velo ity of a parti ular gas omponent and λ is Introdu ing the notation
the mean free path of its mole ules. The diusion oe ient D dened by Dp = δ ξ 2 D1 . (8)
Eq. (2) is the oe ient for free spa e. Sin e λ ∼ 1/P , where P is the gas
pressure, the oe ient in reases as pressure de reases. we write Eq. (7) as
The diusion ux in a porous material is dire ted along the hannels Itot dc
= −Dp . (9)
formed by avities. This pro ess an also be des ribed by Fi k's rst law S dx
Equation (9) whi h des ribes diusion through a porous body has the same
dc
j = −D1 , (3) form as Eq. (1) whi h des ribes diusion in free spa e. The modied
dx
diusion oe ient Dp in Eq. (9) is, however, mu h less than D be ause
where D1 is the diusion oe ient in a narrow hannel. It is not equal to the hannels do not ompletely ll the porous body (note the δ oe ient)
the diusion oe ient in free spa e, as generally the hannel diameter is and the average path of mole ules during the diusion is lengthened (note
omparable with the mole ule free path. The net diusion ux per unit area the ξ oe ient). Besides D1 is less than D.
of the porous medium equals the sum of uxes through all the hannels in Let us now onsider the dependen e of D1 on pressure. Diusion,
a given ross se tion: i.e. a ow of mole ules leading to equalization of on entrations, o urs
due to random motion of parti les in dierent dire tions. The ollisions
X dc X dc of mole ules play here the important role: they hange the dire tion of
Itot = − Si D i ≃− Si hDi . (4)
i
dxi i
dxi mole ular velo ities, entangle their paths, and redu e the rate of diusion.
Equation (2) also des ribes the dependen e of D on λ for the diusion
In Eq. (4) Si is the ross-se tional area of i-th hannel, and the angular through a porous material. However, when evaluating the mean free path,
bra kets stand
P for averaging. Substituting the sum of the produ ts with the we should take into a ount not only the intermole ular ollisions, but the
produ t of Si and the average values of Di and dc/dx we introdu e an ollisions of mole ules with the walls as well:
i
error whi h, however, is small. Noti e that 1
D1 = vλp , (10)
3
dc dc dx dc
= = ξ, (5)
dxi dx dxi dx where λp is the mean free path of a mole ule in a porous medium.
Consider rst the ase of high pressure, when the mole ular free path
where ξ = hdx/dxi i. The x-axis is dire ted along
P the net diusion ux in gas λg is mu h less than the apillary diameter λg ≪ d. In this ase the
through the porous medium. We an also modify Si using the denition intermole ular ollisions are dominant, λp diers only slightly from λg and
i
of porosity δ : the oe ient D1 almost oin ides with D. Hen e when λg ≪ d
P P P
Si xi hxi i Si Si
i i i 1 2
δ=
Sx
≈
Sx
=
Sξ
, Dp = δξ 2 D = δ ξ vλp . (11)
3
At small gas pressures λg ≫ d and the ollisions of mole ules with the in the porous body (the inow is not equal to the outow). Sin e Dp is also
walls of hannels are dominant. In this ase the diusion oe ient in a oordinate-independent, the on entration gradient dc/dx does not depend
porous material be omes: on x either. Hen e, we an write:
1 2 dc c2 − c1
DKp = δξ vd = δξ 2 Dk , (12) = , (17)
3 dx L
where Dk is the Knudsen (mole ular) diusion oe ient for the apillary. where c1 and c2 are the on entrations in the bulbs 1 and 2, and L is the
In the intermediate ase (λg ∼ d) both types of ollisions are equally width of the porous layer (see Fig. 1). A variation of the number of mole ules
important. Let us assume that during one se ond a mole ule ollides z1 in the se ond bulb an be written (using Eq. (9)) as
times with other mole ules and z2 times with the hannel walls. The total
number of ollisions is dN2 c2 − c1
= Itot = −SDp . (18)
z = z1 + z2 . (13) dt L
The distan e traveled by a mole ule per se ond is v , and the mean free path Noti ing that the number of mole ules in the se ond bulb is
in the medium is λp = v/z .
N2 = c2 V2 , (19)
The mole ule mean free path between ollisions with other mole ules
is v/z1 , and the mean free path between ollisions with the walls is v/z2 . plugging it into Eq. (18), and dividing the equation by V2 , we arrive at
The ollisions of mole ules with ea h other and with the walls are almost
independent, hen e dc2 S c2 − c1
v v = −Dp · . (20)
= λg , = λk = d. (14) dt V2 L
z1 z2
Substituting Eq. (14) into Eq. (13), we nd In a similar way we an obtain
1 1 1 dc1 S c2 − c1
= + . (15) = +Dp · . (21)
λp λg λk dt V1 L
Using Eqs. (8), (10), (11), (12), (15), we nally obtain Subtra ting Eq. (21) from (20) we nd

1 1 1 d(c2 − c1 ) SDp 1 1
= 2 + . (16) =− + (c2 − c1 ). (22)
Dp δξ D DKp dt L V2 V1
Integrating this equation over time we obtain

Only the term D ∼ 1/P on the right-hand side of Eq. (16) is pressure-
dependent. For this reason the dependen e of Dp on pressure P is 1/Dp = c2 − c1 = (c2 − c1 )0 e−t/τ , (23)
= AP + B , where A and B are pressure-independent. If the dependen e
Dp (P ) is known one an work out the geometri hara teristi s δξ 2 and d where
of the porous medium. V1 V2 L
τ= . (24)
To measure the diusion oe ient we use two bulbs V1 and V1 onne ted SDp (V1 + V2 )
by the porous body (see Fig. 1). The volumes are lled with gas mixtures
Equations (23) and (24) determine the time dependen e of the dieren e of
of dierent on entrations, the pressures of the mixtures are equal. Using
on entrations in the bulbs.
Eq. (9), we an work out the time dependen e of the on entration dieren e
in the bulbs. First, noti e that in the stationary state the diusion ux jtot Laboratory setup. The s heme of the experimental installation is shown in
does not depend on the oordinate, otherwise the substan e is a umulated Fig. 1. The installation is made of metal; it onsists of two bulbs of volumes
ultimate pump pressure is ∼10−1 torr.

Gauges for measuring the thermal ondu tivity of gases are implemented
for measuring the on entration dieren e in this setup: the thermal
ondu tivity depends on the omposition of gas mixture. Ea h of the
V on entration gauges D1 and D2 is a ylinder (∼1 m in diameter and
D ∼10 m in length) with a thin platinum wire (5·10−3 m in diameter)
stret hed along the ylinder axis. The gauges are in luded in the legs of a
P
bridge ir uit. The resistan es r1 and r2 are almost equal to the resistan es
of gauge wires; the resistors R1 , R2 , and R, shunting r1 and r2 , are used
S
for balan ing the bridge. An ammeter is onne ted to a bridge leg, while a
small onstant voltage is applied to the other leg. A variable resistan e Rg
is onne ted in series with the ammeter to restri t the maximum urrent
through it. The resistors r1 , r2 , R1 , R2 , and R are designed so that at low
D
urrents their temperature and therefore the resistan e remain onstant.
On the ontrary, the wires of the gauges are intensely heated even by
low urrents. The steady-state temperature and resistan e of the wires are
determined by the heat ondu tivity of gas. If the bulbs are lled with
dierent gas mixtures the bridge be omes unbalan ed, the unbalan e value
is proportional to the on entration dieren e.
The dependen e of thermal ondu tivity on gas omposition is rather
ompli ated; however, at low on entrations the bridge unbalan e is dire tly
Fig. 1. Experimental installation proportional to the on entration dieren e. The experiment shows that for
an air-helium mixture the proportionality holds within ∼0.5% a ura y if
V1 = 220 ± 20 m3 , V2 = 220 ± 20 m3 onne ted by a hannel of L = the fra tion of helium is less than 15%.
= 11.0 ± 0.2 mm in length and d = 9.5 ± 0.1 mm in diameter. The hannel During diusion the on entration dieren e de ays exponentially (see
is lled with a porous material P, the sealer R is made of rubber. Eq. (23)), and the gauge readings obey the exponential law as well:
The gauges D1 and D2 measure the on entration, they are mounted on N = N0 e−t/τ , (25)
the installation axis. The gauge D2 is xed while the gauge D1 an be moved
verti ally by a ylindri al s rew nut on the top of V1 . A spe ial up K3 with where N0 is the initial reading.
a rubber seal is atta hed to the bottom of the gauge D1 . By pressing the
up against the bottom of V1 one an separate the bulbs. To prevent air Some features of the applied te hnique should be mentioned:
leakage during a gauge displa ement the gauge is soldered in the bulb V1 by 1. To eliminate thermal onve tion the gauge is made as a long thin
means of a sylphon, a orrugated thin-walled ylinder. The bulbs V1 and V2 verti al ylinder with a heated wire stret hed along its axis. The internal
an be onne ted to a ba king pump or a helium ylinder via the valves K1 avity of a gauge is onne ted to a bulb volume via spe ial openings. The
K7 . A manometer M with a at membrane as a sensitive element is used size of the openings and the gauge volume are spe ially hosen to provide
for pressure measurements. A aving-in of the membrane is dete ted with a high rate of diusion from the bulb to the avity; this rate signi antly
a mirror ree ting a light spot on a s ale. The manometer is dierential- ex eeds the one between the volumes V1 and V2 . Hen e the gas omposition
type, i.e. it measures the pressure dieren e between the opposite sides of in the gauge and the bulb is almost identi al.
a diaphragm. The ex ess pressure se tion of the manometer is onne ted to 2. Due to in omplete energy ex hange between gas mole ules and the wire
the installation. The residual gas is removed from the other se tion by the surfa e the temperature of the latter slightly ex eeds the temperature of the
ba king pump onne ted to the installation via the valves K5 and KM . The adja ent gas layers, whi h results in the ¾temperature drop¿ (see 2.2.2).
Due to this fa t, and also be ause the gauges are not a tually identi al, the the valve K1 and measure the established pressure. Set su h a value of Rg
bridge balan e depends on pressure. Therefore to improve the a ura y of that the ammeter readings are about 90% of the s ale.
the experiment the bridge should be balan ed after lling the installation 8. Open the valve K3 , lose K1 and K2 , start the stopwat h, and register the
with air at working pressure. time dependen e of the ammeter readings. Continue the pro ess until the
initial readings are halved. There must be at least 10 experimental points
LABORATORY ASSIGNMENT in this range.
Familiarize yourself with the gas and ele tri al ir uits of the installation. 9. Repeat the measurements at 34 values of P1 in the range of 10150 torr.
1. Swit h Rg to its maximum value and turn the ammeter on. Turn the 10. When the experiment is over open the valves KM and K4 . This operation
swit h V to power the bridge ir uit; turn the lighting of manometer M prevents the ex ess pressure dieren e from building up in the manometer
on by the toggle T . be ause of leaks in the valves.
2. Start the va uum pump and eva uate both se tions of the manometer M to 11. Conne t the pump to the atmosphere (open K5 ) to avoid extruding va uum
the ultimate pressure. The valve K5 must be set in proper position (towards oil into the installation.
the installation), the valves KM and K4 must be open, and the valves K1
and K2 losed. Find the proper positions of the valves. After the ultimate
va uum is attained (this is indi ated by the "kno king"sound of the pump), TREATMENT OF EXPERIMENTAL DATA
the valve KM should be losed to maintain zero pressure in the manometer 1. Verify that the diusion obeys Eq. (23):
se tion. This pressure should be monitored during the experiment.
3. Conne t the volumes V1 and V2 by opening the valve K3 . Prior to that try c2 − c1 = (c2 − c1 )0 e−t/τ .
to turn the nut ring lo kwise. If the nut does not yield the valve is losed To a omplish this end plot the results of ea h experiment: the time on the
and it should be opened by turning the nut ounter- lo kwise. abs issa and ln(I/I0 ) on the ordinate (here I0 is the ammeter urrent at
N.B. Do not apply mu h eort when losing the valve K3 (rotating t = 0). Draw straight lines through the points.
the nut lo kwise) otherwise it an be broken. To open the valve rotate 2. Cal ulate the slopes of the lines and using the installation parameters work
the nut ounter- lo kwise by 23 turns. If the valve is not opened enough out the diusion oe ients Dp .
the diusion is obstru ted while opening it too mu h leads to sylphon
3. Plot the inverse of the diusion oe ient versus pressure P . Using this plot
overloading.
and Eq. (16), determine the quantity δξ 2 for the given porous medium and
4. Open the valves K1 and K2 and eva uate the installation to P1 ≈ 20 torr. the diusion oe ient in the Knudsen regime DKp . The diusion oe ient
If the pressure is lower than 20 torr one should let the air in to obtain the of helium in air at P = 760 torr equals D = 0.3 m2 /s.
required pressure. For this purpose use the pump avity: make sure that the
4. Cal ulate the average pore diameter d. To do this al ulate the thermal
pump is o, open the valve K5 and open the pump to the atmosphere, then
velo ity of helium atoms and use the previously obtained values and Eq. (12).
onne t it to the installation.
Using this value estimate the pressure orresponding to transition between
5. Balan e the bridge at the working air pressure P1 : rst at the maximum and the Knudsen and vis ous diusion regimes.
then at the minimum value or Rg . After the bridge is balan ed set Rg to the
maximum again. By doing this you preserve the ammeter from overloads Questions
during later manipulations. 1. Prove that the gas on entration is almost uniform in the installation in our
6. Eva uate the installation on e more and lose the valves K3 , K2 . Fill the experiment.
volume V1 with helium up to the pressure of ∼0.1P1 by using the valves 2. What is the dieren e between the Knudsen and vis ous regimes of diusion?
K7 and K6 . If the pressure signi antly ex eeds 0.1P1 eva uate the ex ess Literature
by the pump. Close the valve K1 and eva uate helium from the onne ting 1. Sivu hin D.V. Course of general physi s. Vol. 2. Thermodynami s and mole ular
pipes. physi s. M.: Nauka, 1990. 90, 92, 93.
7. Open the valve K2 . Using the valve K5 ll the volume V2 with air to the 2. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976.
pressure of ∼ 2P1 . Close K4 . Equalize the pressures in V1 and V2 by opening ë. III, 40, 42, 43.
116 TRANSPORT PHENOMENA
3. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001. Chapter III
Ñ. 7880, 8794.
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 235236.
MOLECULAR PHENOMENA
Air and many other gases an be treated as ontinuous media under

standard temperature and pressure. This means that the inter-mole ule
ollisions are more frequent than the ollisions between mole ules and
the walls of bulbs, pipes and other ma ros opi obje ts. Many transport
phenomena in gases (e.g., diusion, vis osity, and thermal ondu tivity) an
be des ribed by the same laws as in the ontinuous media (2.5) (2.7),
nevertheless these phenomena emerge due to the mole ular stru ture of gases
(parti ular expressions are given below). These laws an be applied providing
the mean free path λ of a mole ule (see Eq. (2.4)) is mu h less than the
hara teristi size of d of the bulb. If this riterion is not fullled one should
use other laws whi h take into a ount domination of the ollisions between
mole ules and walls over the inter-mole ular ollisions. The quantitative
riterion is spe ied by the Knudsen number whi h is equal to the ratio of
the mean free path λ to the hara teristi size:
λ
Kn = . (3.1)
d
Depending on the parti ular value of the Knudsen number Kn one an
distinguish several va uum levels: low (Kn ≪ 1), moderate (Kn ∼ 1), and
high (Kn ≫ 1). In low va uum the intermole ular ollisions are dominant,
while in high va uum the ollisions between mole ules and walls determine
the transport properties of the gas.
The mean free path in air under standard onditions equals 0.6·10−5 m.
In a typi al laboratory setup with d ≈ 10 m the pressures over 102 Pa
(1 torr) orresponds to low va uum, the pressures from 102 to 10−1 Pa (1
10−3 torr) to moderate va uum, and below 10−1 Pa (10−3 torr) to high
va uum. If the hara teristi size is small, e.g. in porous materials with
the average pore diameter of the order of 1 µm, the pressure of ten torr
orresponds to high va uum; on the ontrary, for the spa eship size of several
meters only the pressures below 10−5 torr would provide high va uum.
118 MOLECULAR PHENOMENA Chapter III 119
Flow of rareed gas through pipe. Let us onsider a ow of rareed Using P = nkT we an express it via the pressure dieren e P1 − P2 :
gas through the thin pipe of length L and radius r. The density of gas is r r
assumed to be so low that the mole ules do not ollide with ea h other in dM 4 3 2πm P1 − P2 4 3 2πµ P1 − P2
= r = r . (3.5)
the pipe at all. The mole ules ollide only with the pipe walls; sin e the dt 3 kT L 3 RT L
dire tion of velo ity of a mole ule re oiled from a rough wall is essentially
Here P1 and P2 are the pressures near the pipe inlet and outlet, respe tively.
random, one an onsider the ow pro ess as one-dimensional diusion. The
In va uum engineering the amount of gas is sometimes measured in units
velo ity of the re oiled mole ule an hange insu iently, or it an be out of
of P V , whi h is related to the mass of gas via the ideal gas law:
the in iden e plane, or it an reverse its dire tion. If the mole ule velo ity
lies in the plane of the pipe axis after the re oil, the free path will be greater µP V
than 2r. If the re oil o urs in the plane orthogonal to the pipe axis, the M= .
RT
free path will be less than 2r. Thus one an estimate the mole ular mean
free path to be 2r under these onditions. Substituting the mass M into Eq. (3.5) we obtain
In what follows we onsider the ow of a rareed gas through a thin pipe s
as a diusion with the mean free path λ = 2r. The law of diusion for a d(P V ) 4 3 2πRT P1 − P2
= r . (3.6)
mass ux was derived before, see Eq. (2.5). Rewriting this equation in terms dt 3 µ L
of the parti le ux dN/dt we obtain:
To ompare our result with that for a vis ous gas at small velo ity
dN dn ( ompared to the speed of sound), i.e. with a ontinuous ow, we an use
= D S, (3.2) the Poiseuille equation (3) from the lab 2.2.5. The gas vis osity is expressed
dt dx
via mole ular parameters (see Eq. (2.6)). As a result, the Poiseuille equation
where S = πr2 and D is the diusion oe ient. A ording to Eq. (2.5) for ontinuous medium be omes:
D = λv̄/3; substituting λ = 2r into this equation we q
obtain D = 2rv̄/3 r
dM 3π r4 2πm P1 − P2
(here the average mole ular velo ity is used: (2.2) v̄ = 8kT = . (3.7)
πm ). If the ow dt 32 λ kT L
is stationary the parti le ux is onstant along the pipe (as the parti les
do not a umulate or disappear). Hen e, dn/dx = const. Integrating this If we substitute λ=2r into the above equation we would obtain the formula
equation and using the boundary onditions we obtain similar to Eq. (3.5) with a dierent (smaller) numeri al fa tor.
The main dieren e between the expressions whi h des ribe the ow rate
dn n1 − n2 of ontinuous media and that of a rareed gas is that the ow rate of the
= , ontinuous media is proportional to r4 , Eq. (3.7), while that of the rareed
dx L
gas to r3 , see Eq. (3.5). The reason for the dieren e is that in reasing the
where n1 and n2 are the parti le on entrations in the vi inity of the pipe pipe radius one also in reases the mean free path of the raried gas.
inlet and outlet, respe tively, and L is the pipe length. Substituting it into
Eq. (3.2) we obtain
Adsorption. The intermole ular for es are not balan ed on the interfa e
of two phases due to the dierent densities on the opposite sides of the
r boundary, hen e the intermediate layer possesses an ex ess energy, the
dN 4 2πkT n1 − n2 so- alled surfa e energy. The interfa e attra ts not only the mole ules of
= r3 . (3.3)
dt 3 m L the phases being in onta t, but the mole ules of admixtures as well. The
" onsumption"of substan e from the gas phase or the solution by the near-
This equation is referred to as the Knudsen equation. The mass of gas owing
surfa e layer of liquid or solid is alled adsorption.
through the pipe per unit time an be written as (we use dM = mdN )
The adsorption pro ess is a ompanied by the release of heat whi h
dM 4 √ n1 − n2 is alled adsorption heat. The adsorption heat is of the same order of
= r3 2πmkT ; (3.4) magnitude as the ondensation heat of the adsorbed substan e.
dt 3 L
120 MOLECULAR PHENOMENA Chapter III 121
Another important property of adsorption is its inuen e on the surfa e the mixture, moreover some heat is released in this pro ess. Mixing of other
tension of the interfa e. Adsorption de reases the oe ient of surfa e solvents an be a ompanied by absorption of heat. In any ase the heat
tension and therefore the surfa e free energy (otherwise there would be released or absorbed is about one order smaller than the typi al heat of
no adsorption). The substan es whi h an be adsorbed by the surfa e of hemi al rea tions.
a given liquid are alled surfa tants. For example, even a small amount of Solubility depends on temperature. Le Chatelier's prin iple allows one to
soap signi antly de reases the surfa e tension of water; that is why it is relate this dependen e to the heat of solution. If the heat is released during
used as a detergent. dissolving the solubility de reases as temperature in reases. Heating of su h
The rate of adsorption depends on the surfa e density of the substan e a system invokes the pro esses tending to de rease the external a tion. In
being adsorbed. The adsorption an be saturated if the surfa e is overed this parti ular ase some amount of the solute pre ipitates and absorbs heat,
with a monolayer of mole ules. Still, the formation of several layers an so the temperature de reases.
be a hieved by in reasing the pressure of adsorbed substan e. Adsorption
is widely used for puri ation of gases and liquids. For this purposes one
Osmoti pressure. The net movement of solvent mole ules through
an use both arti ial and natural materials with developed surfa e: milled a semipermeable membrane is referred to as osmosis. A semipermeable
rystals, soots, a tivated arbon, et . The surfa e area of su h materials an membrane lets small mole ules of the solvent pass through, but stops the
rea h thousand square meters per gram. bigger mole ules of the solute. Net motion of mole ules, whi h tends to
Let us al ulate the surfa e area of a powder onsisting of spheri al equalize the on entrations, is always dire ted from pure solvent to the
parti les of radius r and density ρ. The net mass of the substan e M = solution. The osmosis keeps going until the in rease of the pressure dieren e
= (4/3)πr3 ρN , the net surfa e of the parti les is S = 4πr2 N , therefore between the omponents rea hes some limit alled osmoti pressure.
S = 3M/(rρ). A ne powder has the large surfa e area even if its mass is Osmoti pressure an be signi ant even at low on entrations of
small. Assuming M = 1 g, ρ = 1 g/ m3 and r = 10−6 m we obtain the net dissolved substan es. For instan e, the osmoti pressure between a sweetened
surfa e area of 300 m2 ! and unsweetened tea ex eeds 2 atm., and in some plant ells the pressure
an vary from 5 to 20 atm., whi h provides an inow of water from the soil
Solutions. Solution is a homogeneous mixture of two or more substan es. to the tops of the trees. It is worth mentioning that apillary for es, whi h
If the amount of one of the substan es ex eeds that of the others, the ould also be large, an not raise water higher than 10 meters sin e the
substan e is alled solvent while the others are alled solutes. A solution natural water an not withstand negative pressure. The swimmers whi h
is spe ied by its on entration whi h an be dened in several ways. One open their eyes underwater also experien e the osmoti pressure as the
should distinguish between the weight, molar and volume on entrations. intrao ular pressure de reases due to inow of water through the ornea.
For instan e, the weight on entration is the ratio of the solute weight to From experimental data we know that the osmoti pressure of a weak
the net weight of the solution. solution of a non-disso iating substan e numeri ally equals the pressure of
Solubility of a substan e in another one is usually limited, i.e. one annot the solute as if it were and ideal gas o upying the volume equal to the
dissolve more than a ertain amount of a solute in a given amount of solvent. volume of the solution. In other words, the osmoti pressure Posm an be
The solution ontaining maximum possible amount of a solute is alled the al ulated from the ideal gas law:
saturated solution and if one adds more solute to the saturated solution
the rst will not be dissolved. The on entration of a saturated solution Posm = nkT, (3.8)
spe ies the ability of the solute to be dissolved in a given solvent; it is
alled solubility. where n is the solute on entration (number of mole ules in unit volume),
Gases under standard temperature and pressure as well as some liquids k is the Boltzmann onstant, and T is the absolute temperature.
(e.g. water and ethanol) an be mixed in any proportions. Solubility of other Equation (3.8) represents the Morse equation; it an be derived theoreti ally
liquids is limited, e.g. water and kerosene almost do not mix. from the thermodynami prin iples.
It is worth mentioning that solutions are not simply "me hani al Using Eq. (3.8) one an determine the on entration of the solute for a
mixtures"of the solvents: they exhibit several properties of hemi al ompounds. given osmoti pressure Posm . If the net mass of the solute is also known,
By mixing ethanol and water we observe a de rease in the net volume of one an nd the relative mole ular mass (provided that the mole ules either
122 MOLECULAR PHENOMENA 2.3.1 123
do not disso iate or split up into a known number of ions). This method of
mole ular mass determination is used in hemistry to study the ompounds C C
whi h an not be obtained in a gaseous form.
It is worth mentioning that the value of Posm for weak solutions is
T
independent both of the type of the solute and solvent mole ules and the T I
stru ture of the semipermeable membrane. HP FB O
HB
2.3.1. Creation and measurement of va uum

Purpose of the lab: 1) to measure the volumes of low-va uum and C
~12 V
C C
high-va uum se tions of the installation; 2) to determine the pumping
rate by two dierent methods.
C
Tools and instruments: a va uum installation with oil manometer,
thermo ouple and ionization va uum gauges.
BP
Depending on va uum quality, va uum installations an be divided into
three groups: 1) low va uum below 10−2 10−3 torr; 2) high va uum
Fig. 1. Experimental installation
10−4 10−7 torr; 3) and ultrahigh va uum 10−8 10−11 torr. In this
experiment one studies ommon te hniques of pumping down to the pressure
of 10−2 torr by means of a displa ement pump and down to the pressure of The valve C1 is used to open the installation and the ba king pump to the
10−5 torr by using a diusion oil pump. The te hniques of va uum quality atmosphere, it should be losed during the experiment. The three-way valve
measurements within this pressure range are studied as well. C2 is used to onne t the ba king pump to the installation or open it to the
atmosphere. The valve C4 onne ts two legs of the oil manometer. It should
Laboratory setup. The installation is made of glass and onsists of a fore-
be open during the experiment ex ept for the measurement of pressure in
va uum bulb (FB), a high-va uum diusion pump (HP), a high-va uum
the low-va uum se tion. The valves C5 and C6 onne t the apillary to the
bulb (HB), oil (O) and ionization (I) va uum gauges, thermo ouple va uum
low-va uum and high-va uum se tions, respe tively. The net volume of two
gauges (T1 and T2 ), a ba king pump (BP) and oupling valves C1, C2, ...,
valves approximately equals 50 m3 (the exa t value is indi ated on the
C6 (1). In addition, the installation is supplied with an autotransformer with
setup), the length and diameter of the apillary equals 300 mm and 0.9 mm,
variable output voltage (or rheostat) and an ammeter to ontrol the heater
respe tively.
urrent of the diusion pump.
Valves. All valves of the va uum installation are made of glass. The valves Ba king pump. The s heme and operating prin iple of the rotary vane-
are thin-walled, the stoppers of the valves are hollow and inseparable from type roughing-down pump are illustrated by 2.
the handles. The stoppers are lapped in their en losures with the va uum The pump rotor is e entri in the ylindri al avity so that its upper
lubri ation used for va uum potting. The openings in the stoppers are visible part remains in tou h with the upper point of the avity. Two blades freely
through the sidewall, so one an easily see whether the valve is open or slide in the slit along the rotor diameter, a spring presses them against the
losed. If there are any ir ular stripes on the stopper, it means that the valve avity walls. The blades divide the volume between the rotor and the avity
is not properly lapped or lubri ated and therefore not airtight. One should in two se tions.
monitor the valves during the experiment. The valves operate properly if the The operating prin iple of the pump is illustrated in Fig. 2 whi h shows
pressure inside them is lower than atmospheri one; in this ase the stopper the su essive positions of the blades during the lo kwise rotor rotation.
is pressed against the en losure. In position "a"the gas from the pumped volume lls in the spa e between
ag repla ements
A
B A A
B B
A
B
a b d
Fig. 2. Operation prin iple of two-blade ba king pump. In positions "a"and
"b"the blade "A"draws the raried air from the pumped volume, while the blade
"B"pushes the entrapped air to the atmosphere. In positions " "and "d"the
blades swap their roles.
the blade "A"and the line of onta t between the rotor and the avity wall.
The rotor rotation in reases the volume of this spa e (see Fig. 2b) until the
blade "B"blo ks the inlet opening (see Fig. 2 ). After the blade "A"passes
the outlet opening and the onta t line (see Fig. 2d), the blade "B"will
ompress the next potion of the gas and pushes it to the atmosphere. One
should keep in mind that after the pump shutdown it should be opened to
the atmosphere. If this is not done the atmospheri pressure an extrude the
~
oil from the pump to the pipes and the va uum system. The pump should Fig. 3. Operation prin iple of diusion pump
be opened to the atmosphere using the valve C1 or C2.
After starting the pump one should wait until it eva uates its own
volume and the volume of the installation separated by the valve C2. One air mole ules approximately equals the width of the annular gap between
an determine when this is a omplished by listening to the sound of the the nozzle C and the pipe walls CC. In this ase the jet of oil steam drags
operating pump: at rst the pump makes a lot of noise, then its sound the mole ules from the whole ross se tion of the gap.
be omes softer and, nally, when the va uum inside the pump is low enough The saturation pressure of oil vapor is mu h greater than 5·10−2 torr at
the pump starts "kno king". the pump operation temperature (whi h is maintained by the heater of the
Diusion pump. The operating prin iple of the diusion pump is based on tank A). For this reason the oil vapor forms a dense jet dragging the gas
trapping (diusion) of air mole ules by a jet of oil steam. The mole ules are mole ules. If the diusion pump is turned on at the pressure omparable
arried by the jet and annot return to the pumped volume. In the vi inity with that of the oil vapor, no jet an be formed: the oil simply oxidizes and
of the jet an area of rareed air is formed, and the mole ules from the volume burns. The diusion pump is not allowed to operate at the pressure above
being pumped are "attra ted"there. The pumping rate of a diusion pump the threshold value marked with the red line on the s ale of the thermo ouple
ex eeds that of a ba king pump by hundreds (and even thousands) times. va uum gauge (∼1.2 mV).
The stru ture of a single stage of diusion pump is s hemati ally shown The diusion pump used in the installation (see Fig. 1) has two stages
in Fig. 3 (in the installation several stages are used). The oil in the tank A is and therefore two nozzles. The rst nozzle is verti al while the se ond one
heated by an ele tri oil. The oil steam rises along the pipe B and es apes is horizontal. Another heater used for oil re ti ation is pla ed after the
from the nozzle C. The jet of oil steam drags the air mole ules oming from se ond stage. The volatile oil fra tions evaporated there are supplied to the
the eva uated volume through the pipe CC. The mixture then omes to the rst stage. The jet of the rst stage is enri hed with volatile fra tions and
verti al pipe D where the oil ondenses on the walls and ows down while hen e it is denser thereby allowing the pumping of the low-va uum se tion
the remaining gas is removed by the ba king bump through the pipe BP. at higher pressures. The se ond stage, in ontrast, is enri hed with heavy
The operation of diusion pump is most ee tive if the mean free path of fra tions. This jet is not as dense as the rst one, and it has a lower oil vapor
saturation pressure. Thus the inow of the oil vapor to the pumped se tion
is redu ed, whi h allows one to reate a higher ultimate va uum ompared P, torr
to the single-stage operation.
Operating the diusion pump implies following ertain rules, otherwise
the installation ould be damaged. In parti ular turning on the pump heater
is allowed only when the pressure in the installation is below 5 · 10−2 torr.
If the pre-va uum is insu ient the oil will be spoiled.
The oil immersed in the oil is heated with
alternating urrent (U ≈ 12 V). The urrent
is ontrolled by means of the autotransformer
in the range of 1 1.5 A. When the heating is
F F
started the pressure in the installation goes up
due to evaporation of the air dissolved in the oil.
Intense evaporation of oil begins after about 10
minutes; this moment is marked by formation
of the lm of ondensed vapor on the walls of
the diusion pump. One should not allow too EMF, mV
T T
intense boiling of the oil. Fig. 5. Calibration urve of LT-2 thermo ouple
Oil manometer onsists of a U-shaped tube
half lled with a vis ous oil with very low
pressure of saturated vapor. Sin e the oil temperature and depend on the rate of heat emission to the environment.
density is rather low (ρ = 0.9 g/ m3 ) one an The rate of heat loss is determined by the thermal ondu tivity of
measure only a small pressure dieren e (up the lament and thermo ouple, the thermal ondu tivity of gas, the heat
to several torr). During the eva uation and transfer by onve tive gas streams inside the bulb and by the infra-red
opening the installation to the atmosphere the radiation of the lament. In a usual operating mode the thermal ondu tivity
valve C4 must remain open to prevent an oil of gas is dominant. At pressures ex eeding 1 torr the thermal ondu tivity
outburst in the installation. The valve C4 is of gas and, hen e, the termo ouple emf are almost independent of the gas
losed only during the pressure measurements. pressure and the gauge does not work.
Due to high vis osity of oil it takes some At high va uum the mean free path of the mole ules be omes omparable
Fig. 4. Ele tri ir uit of the time before the oil level sets. with the lament diameter and the rate of heat loss de reases whi h results
thermo ouple va uum gauge Thermo ouple va uum gauge. The sensitive in in reasing temperature of the jun tion .2 If the pressure falls below
with LT-2 lamp element of this gauge is platinum platinum- ∼10−3 torr, the heat transferred by gas be omes omparable with other
rhodium thermo ouple soldered to a ni kel heat losses and the lament temperature remains almost onstant. The
lament and pla ed in a glass bulb (LT-2 or PMT-2 lamp). The alibration urve of the PMT-2 thermo ouple is shown in 5.
thermo ouple design is shown in Fig. 4. A dire t urrent passes through Ionization va uum gauge. The onstru tion of ionization va uum gauge
the lament F; a potentiometer R ("Filament urrent adjustment") is used is illustrated in Fig. 6. The gauge onsists of a three-ele trode va uum tube.
for setting the value of the urrent. The thermo ouple T is onne ted to Ele trons are emitted by the heated athode and a elerated by ele tri
the terminals of a voltmeter1 whi h readings are determined by the lament eld to the spiral anode. Ele trons passing between the spiral turns are
1 There is only one galvanometer in the thermo ouple gauge. If one sets the toggle as a voltmeter.
swit h to the position "Filament urrent the galvanometer operates as an ammeter 2 The most sharp temperature drop o urs next to the lament at the distan e of
onne ted in series with lament. In "Measurement"position the galvanometer operates several lament radii.
then de elerated by the eld of the olle tor and turn ba k to the athode in units of P V ; one an easily see that this produ t equals the mass of gas up
then ba k to the anode and so on. An ele tron exe utes several os illations to the fa tor of RT /µ. The equation whi h des ribes the eva uation pro ess
between the athode and the olle tor until it is absorbed by the anode. an be written as
During the os illations the ele trons ionize gas mole ules. The ions reated
between the anode and the olle tor are attra ted by the olle tor and −V dP = (P W − Qd − Qe − Qp )dt. (1)
ontribute to its urrent.
The ioni urrent in the olle tor ir uit The left hand side of this equation is the de rement of the gas amount in the
Ionic current is proportional to the gas density and eva uated volume while the right hand side is the amount of gas removed by
measurement junction it an be used to measure the pressure. the pump minus the gas inow for the time dt. When the ultimate va uum
The ionization probability depends on the is rea hed (at the pressure Pu ),
hemi al omposition of gas in the tube
(and hen e in the eva uated volume). The dP
Cathode = 0,
manometer alibration is valid if the gas is dt
air.
Spiral anode (+200 V) and thus
The heated athode fuses if the pressure
ex eeds 1 · 10−3 torr. For this reason before Pu W = Qd + Qe + Qp . (2)
Collector (-50 V)
swit hing on the ionization manometer one From this equation one an obtain the relation between the ultimate pressure
Tube should as ertain that the pressure does and the pumping rate:
not ex eed 10−3 torr a ording to the P
Qi
Cathode heating voltage
thermo ouple manometer. W = .
Pu
Spiral anode During the measurements the lament of
heating voltage
the ionization gauge is heated, whi h an Typi ally Qe is onstant, Qp and Qd are almost time independent and an be
Fig. 6. Ionization gauge LM-2 lead to desorption of the gases from the onsidered as onstants too. Assuming the pumping rate W to be onstant
ele trodes, glass walls of the tube, and the as well one an integrate Eq. (1) and use Eq. (2) to obtain
lament itself. The emitted gas mole ules hange the pressure inside the tube
leading to in orre t readings. For this reason the ionization gauge should be W
P − Pu = (P0 − Pu ) exp − t , (3)
warmed up (degassed) for 1015 minutes prior to the measurements. The V
degassing is done by passing a urrent through the heli al anode.
where P0 is the initial pressure. Typi ally P0 is mu h higher than Pu , so one
Eva uation pro ess. The e ien y of a pump is determined by the an write
pumping rate W measured in liters per se ond. The rate W is the volume

W
of gas removed from a ontainer per unit time at a given pressure. The P = P0 exp − t + Pu . (4)
V
pumping rate of the ba king pump equals the apa ity of the intake plenum
multiplied by the number of rotations per minute. The hara teristi time τ = V /W is the measure of the pumping system
Let us onsider a typi al s heme of the eva uation pro ess. A va uum performan e.
system an be divided into two parts: a "pumped volume"(whi h in ludes Let us now onsider the fa tors whi h determine the pumping rate. The
the experimental installation) and a "pump"(whi h in ludes the tubing and system named previously as "pump"in ludes not only the pump itself but
the valves). We denote the amount of gas desorbed from the walls of the the valves and the tubing onne ting the pump to the eva uated volume as
pumped volume per unit time by Qd ; the amount of gas penetrating into well.
the volume per unit time from the outside through the leaks is denoted by Mathemati al des ription of a va uum system is based on the equations
Qe . The pump itself an be a sour e of gas, we denote the gas ow from the similar to Kir hho's ir uit laws. A pressure dieren e ∆P orresponds
pump ba k to the eva uated volume by Qp . The amount of gas is measured to applied voltage, a gas ow to ele tri urrent, and a ow apa ity
to ondu tivity. Addition of ow apa ities is similar to addition of the Cal ulating the hara teristi s of the va uum systems one should take
ondu tivities3 For the in-series onne tion: into a ount the ow apa ities of the openings (e.g. in the valves). The
1 1 1 1 number of mole ules ν owing out of the opening into va uum in the unit
= + + + ..., (5) time is given by
W Wp C1 C2
1
ν = Snv̄, (8)
where W is the eva uation rate of the system, Wp is the pumping rate of the 4
pump itself, and C1 , C2 , ... are the ow apa ities of the system elements. where S is the opening ross se tion, n is the on entration of mole ules in
Equation (5) shows that ow apa ity of the pipes determines the eva uation the vi inity of the opening, and v̄ is the average velo ity of gas mole ules
rate together with pump e ien y. It is no good to use an e ient pump (2.2).
if the inlet pipes are not wide enough. The rule of thumb is that tubing On the other hand, ν = dN/dt, N = P V /kT , n = P/kT , and, similarly
diameters do not matter mu h in the low va uum se tion and are extremely to Eq. (7), one an al ulate the ow apa ity of the opening:
important in the high va uum se tion. The diameters of pipes in the high
va uum se tion should not be less than the diameter of the pump.

dV v̄
Cop = =S . (9)
Gas ow through a pipe.. The regime of gas ow depends on the ratio dt op 4
of the hara teristi size of the ow to the mole ular mean free path. At
atmospheri pressure and even at the typi al fore-va uum pressure the free The average velo ity of air mole ules at room temperature is v̄/4 =
path is mu h less than a pipe diameter, so the ow regime is determined by = 110 m/s= 11 l/s· m2 .
gas vis osity, i.e. by intermole ular intera tions. At high va uum we arrive Equation (9) an be dire tly obtained from the relation
at a dierent situation: the ollisions between mole ules play a minor role
ompared to the ollisions between mole ules and pipe walls. In this regime v = Cop n,
the ow is similar to gas diusion from the areas of higher on entrations
whi h manifests the equivalen e between the pumping apa ity of the
to lower ones, the mean free path equals a pipe diameter.
opening opened to high va uum and a piston whi h expands the volume
At high va uum (in other words, in the regime of Knudsen ow) the gas
at the rate of Cop (l/s).
ow rate is given by the following equation(3.6):
s Cal ulating the pumping rate of a diusion pump one an assume that
d(P V ) 4 3 2πRT P2 − P1 every mole ule whi h rosses the annular gap between the pump nozzle and
= r . (6) the walls is aptured by the steam jet and never returns to the eva uated
dt 3 µ L
volume. Hen e the pumping rate equals the ow apa ity of the opening with
We an apply this equation to the pipe onne ting an eva uated volume the ross se tion equal to that of the annular gap, i.e. the pump operates as
with a pump. Let us negle t the pressure P1 at the pump end ompared to a gap with the eva uated gas on one side and va uum on the other side.
the pressure P = P2 in the volume. The pipe apa ity Cpipe is then:
s LABORATORY ASSIGNMENT
dV 4 r3 2πRT
Cpipe = = . (7) I. Measurement of the volumes of low-va uum and high-va uum se tions
dt pipe 3L µ
1. Make sure that the valve C4 is open. Open all valves ex ept C1 and C2.
One an see that the pipe apa ity is proportional to the third power of
2. Open the installation to the atmosphere via the valves C1 and C2.
its radius and inversely proportional to its length. For this reason short and
wide pipes should be used in va uum setups. 3. Close the valves C5 and C6 (handles up). About 50 m3 of air at the
atmospheri pressure is " onned"in these valves and in the onne ting
3 One should keep in mind that the analogy between ow apa ity and ondu tivity
apillary (the exa t volume is indi ated on the installation).
is valid only for mole ular ow. In a laminar regime the gas ow rate depends not only
on the pressure dieren e along the pipe, but on the sum of the pressures at the ends as 4. Close the valves C1 and C2, turn on the ba king pump and wait until it
well. eva uates its own volume. Conne t the installation to the ba king pump
(open C2) and eva uate the installation to the pressure of 10−2 torr. Measure 18. Determine the pumping rate by measuring the improvement of va uum
the pressure with the va uum gauge VT-2 onne ted with M1 . quality during the eva uation. To do so:
5. Close the valve C2 (dis onne t the installation from the pump). Stop the a) stop the eva uation of high-va uum se tion ( lose the valve C3) and
ba king pump and open the valve C1. wait until the pressure rises to (59)·10−4 torr;
6. Separate the low-va uum and high-va uum se tions of the installation by b) open the valve C3 and tabulate the readings of the ionization gauge
losing the valve C3. versus time;
7. Get ready the oil manometer for measurements by losing the valve C4. ) plot the results on a graph; hoose the oordinates in whi h the
8. Open the valve C5. The air ¾ aptured¿ in the apillary will be released in dependen e is linear and ompare the result with the predi tions of Eq. (4);
the low va uum se tion and raise the pressure. Measure this pressure with d) al ulate the pumping rate W of the system.
the oil manometer. 19. Estimate the value of Qp :
9. Using the known volume of the " aptured"air (see Fig. 3) nd the volume a) lose the valve C3 to stop eva uation of the high-va uum se tion.
of low-va uum se tion Vf v using the Boyle-Mariotte law. Using the ionization gauge and a stopwat h tabulate the pressure in the
10. Open the valve C3 whi h allows the air from the low-va uum se tion to installation versus time. The measurements should be terminated when the
expand in the high-va uum se tion as well. Measure the pressure with the pressure rea hes the value of (910)·10−4 torr and the valve C3 should be
manometer and al ulate the volume of the high-va uum se tion Vhv . opened to prevent the burnout of the ionization gauge;
11. Open the valve C4. b) using the value of W obtained in p. 18 and taking into a ount that
12. Repeat the measurements from pp. 110. in this ase Eq. (1) reads Vhv dP = (Qe + Qd )dt estimate Qp .
20. Repeat the measurements of pp. 18 and 19. Estimate the ow apa ity of the
II. Creation of high va uum and measurement of pumping rate pipe onne ting the high va uum bulb and the diusion pump and ompare
13. Eva uate the installation using the ba king pump. Make sure that all valves it with the measured value of the pumping rate.
are in su h positions that there are no isolated se tions of the installation. 21. Open the valve C6 and reate the arti ial leak by onne ting the high-
14. If the thermo ouple va uum gauges are o, swit h them on and do not turn va uum and low-va uum se tions via the apillary. The pressure in the
them o up to the end of the experiment. Set the operation values of the tube system should in rease. Measure the stationary value of the pressure Pst
urrents (as indi ated in the equipment erti ates or on the front fa es of and the pressure in the low-va uum se tion.
the gauges). Swit h the thermo ouple manometer to the emf measurement 22. Cal ulate the pump e ien y by using the measured values Pst and Pu . To
mode and measure the pressure in the installation using the alibration do this nd the rate of gas ow through the apillary (Eq. (6)). Let us write
urve. In some gauges both the emf and the orresponding pressure are Eq. (2) for the ases when the apillary is open and when it is losed:
indi ated on the gauge s ale.
d(P V )cap
15. When the pressure drops below 3·10−2 torr lose the valve C6 and start the Pu W = Q1 , Pst W = Q1 + .
high va uum pumping. Turn on the heater of the diusion pump and wait dt
for 10 minutes. Make sure that the oil in the pump started boiling and a Here Q1 is the rate of all leaks ex ept the leak through the apillary.
thin lm of ondensed oil appeared on the pump walls. During operation of Subtra ting one equation from another nd the pumping rate (in the ross
the diusion pump the ba king pump should ontinue working! se tion where the manometer is mounted).
The readings of the manometer M1 should be around 10−2 torr, while Compare the obtained value of pumping rate W with that one obtained
the readings of M2 should rapidly in rease. If the manometer alibration is in p. 18. Explain why the results dier.
orre t the pointer should rea h the end of the s ale. 23. Turn the setup o:
16. Turn the ionization manometer on in a ordan e with the instru tions on a) swit h o the heating of the ionization gauge (turn the swit h
the desk. "Heating") and wait for 12 minutes until the tube ools down. Unmount
17. Measure the ultimate pressure Pu in the system and write it down. At the fuse and return it to the instru tor or laboratory assistant;
P < 10−4 torr make sure that the alibration of manometer M2 is orre t, b) swit h o the heating of the diusion pump and wait till the oil ools
otherwise report to the lab instru tor that a orre tion is required. down (∼10 minutes);
) dis onne t the installation from the ba king pump by losing the valve Glass Metal Nylon
C2. Do not let air enter the installation; 10−9 10−8 10−9 10−10 2·10−8
d) the pressure in ea h se tion of the installation must be equal, hen e,
the readings of the gauges M1 and M2 must be equal as well. If they dier 4. Reverse diusion from diusion pumps. Maximum ratio of output and input
one should adjust the manometer M1 using the readings of M2 (the latter pressures:
is already alibrated at high va uum);
e) stop the ba king pump and open it to the atmosphere by opening the H2 He N2
valve C1. Do not let air enter the installation. 103 104 104 105 107
f) turn o the va uum gauges using the tumblers "Power".
Questions
1. At whi h ir umstan es are the thermal ondu tivity and vis osity of gases
independent of pressure? 2.3.2. Experimental study of ion pump
2. Why are the readings of the thermo ouple va uum gauge almost onstant at
pressures below 10−4 torr? Purpose of the lab: 1) to register the dependen e of ion urrent in
3. For whi h purpose do the ele trons exe ute the os illatory motion in the ionization ionization va uum gauge on time during the eva uation pro ess 2) to
gauge? determine the total number of parti les absorbed by olle tor during the
4. Why is the ow apa ity of pipes in Knudsen regime independent of the size of urrent stabilization
mole ules?
Literature Tools and instruments: LM-2 or PMI-2 va uum tube; VIT-2 va uum
1. Áåëîíó÷êèí Â.Å., Çàèêèí Ä.À., Öèïåíþê Þ.Ì. Îñíîâû èçèêè. Ò. 2. Êâàí gauge; a plotter; and a alibrator.
2. S.E. Frish, A.V. Timoreva. Course of general physi s. Vol. 1. Physi al basi s of
Va uum pumps are used to remove gases from a given volume. To obtain
me hani s. Mole ular physi s. Os illations and waves. M.: Physmathgiz, 1962. pressures above 10−3 torr one usually employes me hani al ba king pumps,
Ch. VII, 5055. while to obtain lower pressures diusion pumps have been ommonly used
3. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976. until re ently. In these pumps gas mole ules are removed by a stream of oil
ë. 57, 59. vapor; the saturated vapor pressure of oil used for this purpose is rather
4. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001. small (< 10−7 torr) at room temperature.
Ñ. 86, 9293. In re ent years new te hniques of eva uation have be ome widespread,
5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1. among them there are sorption pumping1 and ion pumping. In sorption
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 226227, 234236. pumps mole ules are aptured by an appropriate sorbent (a substan e with
highly developed surfa e) or by atoms of a metal (typi ally titanium) whi h
Appendix. Properties of gases is vaporized and then ondensed on the pump walls. In ion pumps the
gas mole ules are ionized and a elerated by ele tri eld whi h drives
1. Mean free path of nitrogen mole ules at room temperature: them into the walls of the athode. Quite often both phenomena are used
simultaneously (ion-sorption pumps).
P, torr 760 1 10−1 10−2 10−3 10−4 10−5
1 Sorption is the pro ess of apturing a liquid or gas ( alled sorbate) from the
λ, m 6·10−6
5·10 −3
5·10
−2
5·10 −1
5 50 500
environment by a solid body or liquid ( alled sorbent).
2. Saturation vapor pressure of oil used in diusion pumps ∼10−7 10−10 torr (at
Absorption is the pro ess of apturing a gas by the bulk of liquid or solid (absorbate).
Adsorption is the pro ess of apturing a liquid or gas substan e by the interfa e
room temperature). between the substan e and a liquid or solid (adsorbent), see p. 119.
3. Gas release rates (mainly CO and H2 O) from dierent materials after several Desorption is the pro ess of removal of a substan e from the surfa e of adsorbent;
hours of eva uation (measured in torr ·l/( m2 ·s)): this pro ess is a reverse of adsorption.
In this parti ular experiment one studies the phenomena o urring depends on the ion energy, the ratio of the ion mass to the mass of target
during the pro ess of ion pumping (ele tri pumping). The va uum tube atoms; it is also strongly ae ted by the quality of target surfa e, its porosity,
of ionization va uum gauge is used as a pump and a manometer at the same the amount and type of impurities. In our experiment this oe ient is
time. The tube is s hemati ally shown in Fig. 6 (see 2.3.1). It onsists of a between one and ten.
lament, a sparse heli al anode wound around the lament, and a ylindri al Besides the sputtering of target atoms there is a signi ant probability
olle tor. The ele trodes are mounted in a glass bulb eva uated down to the for the in ident mole ule to es ape the olle tor surfa e. Taking this into
pressure of ∼10−8 torr. a ount one an easily understand why the oe ient of ion adheren e βi
The ele trons emitted from the hot wolfram athode and a elerated by is less than unity. As the ion energy in reases βi → 1 be ause a deeply
the eld of the heli al anode pass between its turns, but they annot rea h embedded ion annot es ape. In our experiment βi ∼ 10−1 .
the olle tor as its potential is lower than that of the athode. Thus the The mi roexplosion also results in emission of ele trons and ions. Both
ele trons de elerated by the olle tor turn ba k, pass between the spiral the bombarding parti les and the target atoms are ionized when emitted
turns again, and so on. As a result, the ele trons exhibit os illatory motion from the olle tor surfa e. These pro esses determine the oe ients of
and go a long path before olliding with the anode and ontributing to the se ondary ion-ele tron and ion-ion emission. In our experiment the rst
athode-anode urrent (emission urrent). On their way they an ionize the oe ient is 610−1 , while the se ond one is even smaller; in what follows
mole ules of residual gas in the tube. we will not take these pro esses into a ount.
If the ionization o urs between the heli al anode and the olle tor the The sputtered atoms an settle on the surfa e, moreover, they exhibit
ele tri eld attra ts positive ions to the olle tor. The ioni urrent appears high hemi al a tivity and an bind the mole ules of all residual gases but
to be proportional to the on entration n of mole ules in the tube: the inert ones. This is the so- alled getter a tion of ion pump. The number
of aptured mole ules per se ond is proportional to the number of sputtered
I atoms and, hen e, to the ion urrent. The proportionality onstant between
= wn. (1)
q the number of absorbed atoms and the ion urrent is alled oe ient of
Here q is the ion harge. For ele tron energies at hand only one ele tron is getter adhesion βg .
usually removed in an ionization a t, hen e q = 1.6 · 10−19 C. The fa tor w As the olle tor surfa e be omes saturated with the residual gas, the
depends on the type of mole ules, geometry of ele trodes, and the applied urrent-stimulated desorption be omes important. When the number of
voltage. For the residual gas and the ele tri onditions in the va uum gauge gas mole ules a umulated on the olle tor is N , the number of mole ules
desorbed per se ond equals CN I/q where C is a oe ient.
VIT-2 w = 2.0 m3 /s.
Bringing all the pie es together we an write the number of mole ules
If every ion approa hing the olle tor were permanently embedded in its
adsorbed by the surfa e per se ond:
walls the left-hand side of Eq. (1) would be equal to the number of mole ules
removed from the eva uated volume per se ond. The term w, in turn, would I
Ṅ = (βi + βg − CN ) . (2)
be equal to the e ien y of the ion pump. The e ien y dened in this way q
is alled "geometri e ien y"; it equals the number of mole ules removed
The rst two terms in round bra kets determine the e ien y of adhesion,
from the tube with the gas on entration n by the displa ement pump whi h
the last one orresponds to desorption pro ess. If the ion pump operates for
plunger in reases its volume by w liters per se ond.
a long time the dynami equilibrium is a hieved and Ṅ tends to zero. We
As a matter of fa t, the ion ollision with the olle tor surfa e is a
denote the equilibrium number of mole ules in the olle tor walls as N∞ ;
ompli ated phenomenon. The embedding of ion into the olle tor resembles,
then setting t → ∞ in Eq. (2) we obtain
to some extent, a mi roexplosion. This is not surprising if one ompares the
ion energy (≈200 eV) with the vaporization heat of the targeted atoms βi + βg = CN∞ .
(ni kel) ≈0.4 eV. Of ourse, the total number of "vaporized"atoms does not
Solving this equation for C and substituting it into Eq. (2) we have
equal 200/0.4 = 500 sin e the energy of the in ident ion is mostly dissipated.

The average number of atoms es aping the bombarded surfa e per one N I
in ident ion is alled oe ient of athode sputtering α. The oe ient Ṅ = (βi + βg ) 1 − . (3)
N∞ q
where
N
I ε = (βi + βg ) 1 − . (6)
N∞
I0 We an see from Eq. (6) that ε de reases during the eva uation pro ess.
Initially there is no gas in the olle tor walls (N = 0), hen e,
ε 0 = βi + βg . (7)
I1
PSfrag repla ements Thus the total adhesion oe ient equals the initial value of ε. Dierentiating
Eq. (6) we nd that
I2 βi + βg ε0
N∞ = − =− . (8)
dε/dN dε/dN
τ We an express ε as a fun tion of urrent I and its derivative I˙. To

τ1 τ2 a omplish this we substitute Ṅ found from Eq. (4) into Eq. (5):
Fig. 1. Method of graphi al dierentiation for two points of the V I˙
urve I(t) orresponding to ion urrents I1 and I2 ε=− . (9)
wI
Equations (1) and (3) are insu ient for des ription of ion pumping be ause By measuring the dependen e I(t) and evaluating I˙ by means of
they ontain three unknown variables N , n and I . Let us try to nd one graphi al dierentiation one an determine the value of ε at any given
more relation. moment. In parti ular, its initial value equal to βi + βg an be obtained.
If the initial on entration of mole ules in the tube with a lean surfa e The method of graphi al dierentiation is illustrated in Fig. 1; it should be
is n0 and N mole ules are settled on the olle tor during the pumping, then: lear that
V 1
ε= . (10)
N = V (n0 − n), wτ
Now let us transform Eq. (8) whi h ontains the quantity dε/dN . We
where V ∼ 100 m3 is the tube volume. Substituting the parti le on entration express this quantity via the dependen e of ε on I whi h an be determined
n from Eq. (1) into this relation we obtain from the data. Using Eq. (4) we nd
V dε dε dI qw dε
N= (I0 − I). (4) = =− .
qw dN dI dN V dI
Substituting this into Eq. (8) and taking into a ount Eq. (7) we nd
Hen e we have found the required equation. The system of Eqs. (3) and
(4) an be integrated but the result is ompli ated and not very illustrative. ε0 V
Instead of obtaining the exa t analyti al solution let us show how the N∞ = . (11)
dε/dI qw
oe ient of total adhesion βi + βg and N∞ an be determined from the
experimental data. Equation (11) allows one to determine N∞ from the data. To obtain
Let us rewrite Eq. (3) as dε/dI one has to plot ε versus I . A ording to Eq.(11) this dependen e must
I be represented by a straight line, whi h is obvious sin e the onstant N∞ an
Ṅ = ε , (5) be obtained from dε/dI for any value of I . Dividing N∞ by the olle tor area
q
S = 20 m2 we an determine the equilibrium surfa e density of mole ules

at the end of pumping. It is useful to ompare this value with the surfa e
density of parti les forming a ontinuous monoatomi layer ∼1015 m−2 .
During the eva uation pro ess the on entration of gas mole ules n in the
va uum tube de reases signi antly. However, it never vanishes sin e there
always exists the reverse ow of gas from the olle tor walls to the eva uated
volume. The ultimate va uum depends on the amount of gas adsorbed in
the olle tor. In real ion pumps the olle tor is degassed prior to pumping
and the emitted gas is removed from the setup, while in our experiment it
is left in the eva uated volume. Fig. 3. Auxiliary unit
2. Pla e a blank sheet of paper on the plotter. To a omplish this shift the
pen-holding bar of the unit I to the rightmost position by the knob 3, put
12 a new sheet and smooth it out. Return the pen-holding bar to the initial
position.
3. Press the paper to the plotter surfa e. To do so set the knob 7 of the unit III
of the plotter in the position ¾Pap¿ and smooth the paper out on e more.
4. Get the va uum tube ready for the experiment: set the knob "Operation
type"of VIT-2 in the "Setting emission urrent"position. It is important
Fig. 2. Plotter ¾Endim 62002¿
sin e otherwise a strong pulse of urrent is generated by the amplier when
A sealed va uum gauge LM-2 (or PMI-2) is used in our setup. Its power is applied to the tube; it an damage the ammeter. Swit h the VIT-2
ele trodes are onne ted to the ir uit of VIT-2 va uum gauge. The VIT- va uum gauge on by the knob "Power 220 V".
2 gauge provides the heating of both athode and heli al anode. The 5. Swit h on the tube heater by setting the knob "Heating"in the upper
measurement of total urrent is performed by an analog ammeter via the position. Using the emission regulating knob set the pointer in the middle
amplier of VIT-2 va uum gauge. Time dependen e of the urrent is drawn of the s ale. Set the knob "S ale fa tor"in position 1.
by a plotter onne ted to the amplier output; the diagram of the plotter 6. Set the "zeros"and the operating range of the plotter. To do this set the pen
ontrol unit is shown in Fig. 2. There is an auxiliary unit in the ir uit at the origin of "X"and "Y"axes using knobs 3 of the units I and II. To
onne ting the va uum gauge and the plotter, its s heme is depi ted in set the deviation range along the Y-axis set the knob of the auxiliary unit
Fig. 3. The maximum output signal supplied by the va uum gauge to the in the "Calibration"position. Press the button K and without releasing it
plotter is 10 mV; it orresponds to the full s ale of the ammeter of VIT-2. It shift the pen up to the mark 25 along the Y-axis using knob 2 of the unit II
is rather di ult to reate the appropriate onditions in the LM-2 tube in (during this operation knob 4 of this unit should be at the position 0,1 or
order to a hieve permanent full-s ale dee tion of the ammeter pointer. The 0,2). Release the button K; the pen should return to the initial position. Set
auxiliary unit allows one to maintain su h a signal permanently. To do this the knob of the auxiliary unit in the "Measurement"position.
one has to set the toggle swit h T to the position ¾Calibration¿ and press 7. Turn the knob "Operation type"of the VIT-2 gauge to the "Measurement"position.
the button K. The button is self-releasing, i.e. the battery B is onne ted Choose the s ale range using the knob "S ale fa tor"in order for the readings
to the supply ir uit only when the button is pressed; when the button is to be between 10 and 100 s ale graduations. If the plotter is properly
released the ir uit is broken. adjusted the pen displa ement is proportional to the deviation of the
LABORATORY ASSIGNMENT ammeter pointer (the full-s ale deviation orresponds to the mark 25 of
1. Swit h the plotter on: turn the knob 8 of the unit III of the plotter (see Fig. the plotter). If the proportionality is not observed repeat 6.
(2)) lo kwise. The indi ator ¾Power¿ should be ashing. 8. Che k operation of the sweeping unit of the plotter. Set the knob "S ale
fa tor"in the "Zero adjustment"position, set the sweep speed of the plotter 2. Would the va uum in rease or de rease if the ion pumping were a ompanied by
at 0.5 s/ m, and press the buttons 10 and 9. The indi ator 12 should be ooling of the olle tor?
ashing and the arriage should start moving. After the pen rea hes the Literature
rightmost position it returns to the initial position automati ally. To start
1. Landau L.D., A hieser A.I., Lifshits E.M. Me hani s and mole ular physi s.
the sweep one more time one should press the button 9 again.
M.: Nauka, 1969. Ch. XII, 95.
9. Swit h o the tube heater: set the "Heating"knob of the VIT-2 gauge in the
"O"position and set the swit h "Operation type"in the "Degassing"position.
The tube spiral will heat the olle tor and the glass bulb, so the major
part of the adsorbed mole ules will be released to the tube volume. The 2.3.3. Measurement of osmoti pressure
re ommended duration of degassing is 510 minutes.
Purpose of the lab: 1) to measure osmoti pressure at dierent
10. Re ord the eva uation urve: set the sweep speed at 10 s/ m, set the knob on entrations of potassium ferro yanide; 2) to verify the van 't Ho's
"Operation type"in the "Measurement"position and swit h on the tube (Morse) law.
heater. Set the knob "S ale fa tor"in the position 10−2 . If the plotter pen
goes o-s ale set the knob "S ale fa tor"in the position 10−1 , wait until the Tools and instruments: an osmometer; a stopwat h; a funnel; a
ammeter pointer goes down to ∼12 graduations (total number of graduations measuring jar; and a beaker.
is 100), set the s ale fa tor at 10−2 again, and, after the plotter pen goes
in-s ale, press the button 9 of the plotter. When the arriage rea hes its In this experiment we study the properties of semipermeable partitions
terminal position, it returns to the initial position automati ally. Turn o (membranes) whi h are permeable to one type of mole ules and impermeable
the tube heater, press the button 9 and draw the line of zero readings. The to another one. For example, water mole ules pass freely through the ell
latter operation is performed at the sweep speed of 0.5 s/ m. membranes of plants and animals but mole ules of a higher mole ular mass
annot. There are also arti ial semipermeable partitions, e.g. ollodion
11. Repeat the experiments 9 and 10 on e or twi e.
and ellophane membranes, et . Solvent penetration through a partially
12. Turn o the setup and treat the experimental data. Perform the graphi al
permeable partition is alled osmosis.
dierentiation (as illustrated in Fig. 1) dire tly on the graph of I(t) urve.
Consider a vessel divided in two parts by a
It is su ient to plot the tangents to 10 points of the urve. Work out the
semipermeable membrane, one part being lled
values of τ from the tangents (keep in mind that V = 100 m3 , w = 2 m3 /s,
with water and the other one with water solution
and the sweep speed is v = 10 s/ m) and using Eq. (10) plot the dependen e
of a substan e whi h mole ules annot pass
ε(I). The dependen e of adhesion oe ient ε on the ion urrent I should be
through the membrane (see Fig. 1). Both parts
represented by a straight line, however, the points orresponding to small
are initially lled to the same level. Experiment Solution
and large urrents an be o the line. This o urs due to the following
shows that water penetrates into the volume
reasons: when pumping starts (at I ≈ I0 ) the tube is ooled after the Water
o upied by the solution. This prosess ontinues
degassing and the ion pumping is a ompanied by sorption on the ooled
until a ertain level dieren e is a hieved; the
surfa es, whi h results in the in rease of ε. At I ≪ I0 , i.e. lose to the end of
orresponding pressure dieren e on both sides
pumping, the urrent-independent thermal desorption an not be negle ted
of the membrane is alled osmoti pressure of the Fig. 1. Dieren e of uid
anymore, whi h results in de rease of ε.
solution. levels aused by osmoti
Using the slope of the ε(I) urve and Eq. (11) al ulate the total number The osmoti pressure obeys Eq. (3.8) (van 't pressure
of mole ules absorbed by the olle tor during the pro ess of ion pumping.
Ho equation):
Using the obtained value of N∞ al ulate the number of mole ules per unit
Posm = nkT, (1)
area of the olle tor surfa e at the end of pumping.
where n stands for on entration of mole ules of the solute, k is the
Questions Boltzmann onstant, and T is the absolute temperature. Using Eq. (1) one
1. What is the highest va uum obtained in the LM-2 tube in this experiment? an derive the on entration of the solute from the value of Posm .
Laboratory setup. A devi e for measuring osmoti pressure is alled

osmometer. Penetration of a solvent through a semipermeable membrane
is a slow pro ess, so it takes a long before the solution-solvent equilibrium is
a hieved. To speed up the measurement the solution is put under an ex ess
air pressure. If the extra pressure is equal to the osmoti pressure, a ow of
the solvent through the membrane eases. If it ex eeds the osmoti pressure
the solvent ows in the opposite dire tion. Thus to determine the osmoti
pressure one an measure the equilibrium gas pressure.
The layout of the osmometer used in the experiment is shown in
Fig. 2. The solution is poured into a ontainer whi h is then pla ed into
a vessel lled with solvent. The ontainer 1 is a ube whi h four lateral
sides are overed with semipermeable ellophane membranes 3 (lms) (a
membrane is 0.2 mm thi k). The membranes are pressed against the walls
by metal meshes 4. Rubber gaskets 7 are inserted between the lms and the
water level walls. Prote tive meshes 4 preserve the lms from inating outwards. The
ontainer is being lled with solution through an opening in the ube bottom
salt solution and plugged with metal s rew 6 with rubber gasket 24. Glass apillary 14
(the inner diameter is 0.5 mm) passes through the ube lid.
Due to osmosis the volume of the solution in reases and liquid level in
the apillary moves up. The elevation rate de reases in the presen e of an
ex ess air pressure in the apillary; the pressure is reated by means of a
rubber dou he 23 equipped with a valve 25 and a glass tap 22. The pressure
Fig. 2. Osmometer is measured with a manometer 21. The tap 22 also helps to release an ex ess
pressure.
1. Container for solution of salt. 13. Spring.
There is a devi e mounted on the top of the ube 1, whi h onsists of
2. Vessel with distilled water. 14. Glass apillary.
orrugation 10, sleeve nut 11, s rew 12, and spring 13, used to adjust the
3. Cellophane membrane. 15. Metal housing of the apillary.
inner volume of the ube. This is ne essary if the membranes stret h during
4. Prote tive mesh. 16. Sleeve nut of the housing.
the measurements and solution level in the apillary drops. Tightening the
5. Hold-down s rew. 17. Rubber tube (sealing gasket).
s rew 12 redu es the ontainer volume thereby expelling the solution into
6. Inlet for solution with plug. 18. Metal washer.
the apillary. In so doing the liquid level in the apillary an be set at a
7. Rubber gasket. 19. Mobile rubber plug for fastening the
apillary. onvenient height.
8. Opening through whi h the solution
enters apillary. 20. Rubber hose. Determination of Posm onsists in measuring the elevation rate v of the
9. Metal plug driven into ontainer 21. Pressure gauge. liquid level in the apillary versus the ex ess air pressure P and plotting
asing. 22. Triplex glass tap. the dependen e v(P ). The greater the pressure dieren e P − Posm , the
10. Corrugated surfa e. higher is the rate v . For P ≈ Posm the rate tends to zero. That is why the
23. Rubber dou he for reation of ex ess
11. Sleeve nut for oarse adjustment of external pressure. measurements should be arried out either for P ≫ Posm or for P ≪ Posm .
vessel volume. 24. Rubber gasket.
12. S rew for ne volume adjustment.
The value of P at whi h v = 0 (i. e. Posm ) an be easily obtained from the
25. Valve hart.
The aim of the present experiment is to measure the osmoti pressure of
water solution of potassium ferro yanide K4 Fe(CN)6 at dierent on entrations
and to verify the van 't Ho's law.
Potassium ferro yanide mole ules dissolve in water as: must be negative (the level drops) and high. For P ∼ 0, i.e. P < Posm , the
rate is high and positive (liquid level rises). Plot the pressure P as abs issa
K4 Fe(CN)6 → 4K+ +[Fe(CN)6 ℄4− . and the level rate v as ordinate and draw a straight line through the points.
The inter ept with the abs issa gives the value of the osmoti pressure. It is
K+ ions penetrate freely through the membrane and do not ause any meaningless to perform measurements at a pressure lose to Posm be ause
osmoti pressure. the rate tends to zero and theoreti al duration of the experiment tends to
innity.
LABORATORY ASSIGNMENT 6. After ompletion of the rst experiment, pour the solution from the
1. Remove the ontainer from the vessel with distilled water. ontainer rst into the beaker and then to a graduation ylinder and noti e
2. Fill the ontainer with a given solution onsisting of 3 grams of potassium the liquid level in it. Pour the solution ba k into the beaker and add to it the
ferro yanide K4 Fe(CN)6 ×3H2 O per 1 litre of water that is suitable for same volume of distilled water. Fill the ontainer with the obtained solution
measurements at a pressure of 0.5 atm in the ontainer. Before lling the (whi h on entration is now redu ed by half). Repeat the measurements
ube he k positions of the sleeve nut 11 and the s rew 12 used to adjust a ording to 25.
the ontainer volume. The nut 11 should be ompletely tightened and the 7. Dilute the solution twi e and measure the orresponding values of Posm .
s rew 12 should be almost undone. Put the rubber stopper on the apillary
to prevent the liquid from leaking out during lling. Turn the ontainer 8. After you have nished the measurements empty the ontainer, unplug
upside down so that the opening 6 is on the top and using a funnel pour the the inlet, and pla e it into the vessel with distilled water. The membrane
solution through the inlet. The ontainer should be lled to the brim. Close windows should be under water.
the inlet with the s rew plug and the gasket. Tighten it up using a wren h 9. Pro ess the data obtained, plot the dependen e of osmoti pressure on the
but do not squeeze the gasket out of the plug. Put the ontainer ba k into on entration.
the vessel and take o the stopper from the apillary. 10. Evaluate the errors of the results.
3. Put the rubber hose 20 on the apillary (dampen the hose tip with water Note. To hange the apillary (this is done either by a laboratory
before putting it on; rstly, to make the joint air proof, and se ondly, to assistant or under her supervision) one should uns rew the sleeve nut 16
fa ilitate taking the hose o). Turn the tap 22 to onne t the dou he with the and unmount the metal housing together with the apillary 14, the rubber
hose. Create an ex ess pressure of ∼200 graduations of the pressure gauge 21 tube 17, and the washer 18. The tube and the washer should then be put
using the dou he, then lose the tap. Make sure that the preset pressure does on the new apillary and inserted into the orresponding opening of the
not hange with time. If this is the ase, start the measurements. ontainer. Bottom edges of the tube and apillary should oin ide. The
4. Set the liquid level approximately in the middle of apillary s ale using length of the apillary should ex eed that of the housing. Then one should
the s rew 12. If air bubbles and/or drops of liquid are observed along the put the metal housing on the apillary and tighten the aptive nut to fasten
apillary the liquid olumn should be pushed down into the ontainer volume the apillary safely in the ube opening.
by loosening the s rew 12. Then it should be fasten ba k, so that the liquid is Then the upper edge of the apillary is fastened with a rubber plug 19
extruded to the initial level in the apillary. If the olumn is not homogeneous whi h is moved inside the housing until the upper edges of both oin ide.
try again. Then one should ut the protruding part of the apillary using a broa h le
5. If the liquid level in the apillary is set properly and the readings of the and break it o. Finally the plug is pushed deeper inside the housing to
manometer 21 do not hange, pro eed with measurement of the level rate enable one to x the rubber hose 20 or a stopper on the apillary.
using stopwat h. Measure 35 points orresponding to a level displa ement When the system is pressurised with the dou he and a ertain pressure
by 12 m. Using the tap 22 redu e the pressure by 2040 graduations of is se ured by the tap one should he k whether the hose- apillary joint is
the manometer and repeat the measurement of v . Wait 12 minutes after airtight. If you spot a pressure alteration on the manometer you should nd
redu ing the pressure to allow the membranes to take their equilibrium the leak. This an be easily done by bending dierent parts of the exible
shape. Next measurements should be arried out at pressures of ∼40 and tubing one by one starting with the manometer inlet: this isolates ertain
0 graduations. At large pressures (∼200 graduations) P > Posm , so the rate se tions of the installation.
Questions Noti e that ionization pro ess is dierent from ex itation pro ess in this
1. Estimate the inuen e of the apillary ee ts on the results of the measurements. respe t. In ionization the energy is partially spent on kno king an ele tron
2. For whi h on entration of the solution is Eq. (1) valid? from an atom and a elerating it and thereby ontributing to the kineti
energy of the kno ked ele tron. Kineti energy of a free ele tron an take
Literature any value, so the kno ked ele tron an re eive any energy between zero and
1. Ëàíäàó Ë.Ä., Àõèåçåð À.Ï., Ëèøèö Å.Ì. Ìåõàíèêà è ìîëåêóëÿðíàÿ èçè the energy of the in ident ele tron minus the ionization energy.
êà. Ì.: Íàóêà, 1969. 80.
If one ould dire t in ident ele trons to a ertain atomi shell it would be
2. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. II. Òåðìîäèíàìèêà è ìîëåêóëÿðíàÿ
the best option. However this is impossible. Therefore in a real experiment
èçèêà. Ì.: Íàóêà, 1979. ë. XI, 124.
one inevitably averages the results obtained in s attering the ele trons with
dierent impa t parameters.
The probability of ele tron s attering is determined by measuring the
2.3.4. S attering the slow ele trons on mer ury mean free path whi h an ele tron travels between intera tions. It is even
atoms better to dene this probability by spe ifying the ross-se tion of the pro ess
studied (this on ept is dened below).
Purpose of the lab: 1) to measure the dependen e of olle tor urrent
In this experiment the ross-se tion of s attering the slow ele trons on
on temperature; 2) to al ulate the ross-se tion of ele tron s attering on
mer ury atoms is determined. Here slow ele trons are the ele trons whi h
mer ury atoms.
energy is not su ient to ionize atoms.
Tools and instruments: an experimental installation; a thermostat; two Consider a beam of parti les (in our ase
sour es of voltage; an ammeter; two mi roammeters; and a voltmeter. ele trons) passing through a medium (see
x ∆x
Fig. (1). Consider a layer of PSfrag
small repla
widthements
dx
Passage of free ele trons through matter is of great interest both from at the distan e x from the surfa e. Let the
theoreti al and pra ti al perspe tive. Ele trons passing through atoms number of parti les rea hed the depth x beN0 N (x) N (x + ∆x)
intera t with their ele tron shells and parti ipate in elasti and inelasti N (x). Due to intera tions in the layer dx the
ollisions. number of parti les N (x + dx) rea hed the
In elasti ollision an ele tron transfers almost no energy to the medium. depth x + dx is less than N (x). The number
An ele tron intera ting with an atom as a whole is being s attered by the of parti les intera ted in the layer is dire tly Fig. 1. Derivation of Beer
obje t whi h mass is several thousand times greater than ele tron mass. An proportional to the initial number of parti les Lambert law
ele tron boun es ba k from an atom like from a solid wall, so its dire tion N , the mole ular density n in the layer, and to
of motion hanges but its kineti energy is almost onserved. the layer width dx, so
In inelasti ollision ele tron energy de reases: it is spent on ionization
N (x) − N (x + dx) = σnN (x)dx,
or ex itation of atoms moving toward the ele tron. To ionize atom ele tron
must have enough energy sin e atomi ele trons are tightly bound. To where σ is a oe ient of proportionality. Dividing this equation by dx and
remove even an external ele tron the energy transfer must be about ten sending dx → 0 one nds
ele tron-volts1. In nitrogen and oxygen this energy is about 14 eV.
1 dN (x)
To ex ite an atomi shell several ele tron-volts is usually su ient. A = −σn. (1)
shell being ex ited an re eive only a denite portion of energy from a N (x) dx
passing ele tron, whi h equals the energy dieren e between the nal and If σ and n are independent of x, this equation an be easily integrated:
initial atomi states. (Ele tron energy in atom is quantized, i. e. it an a ept
only a dis rete set of values). No other energy an be transferred to atom. N (x) = N (0)e−σnx . (2)
1 1 eV = 1.6 · 10−19 J is the energy of ele tron a elerated by the potential dieren e Therefore the number of parti les in the beam de reases exponentially as it
of 1 V. passes through the medium. This equation is alled Beer-Lambert law.
dN/N , is equal to the ratio of this area to S :

r1
dN
= −π(r1 + r2 )2 ndx.
N
r2
Comparing this equation to Eq. (1), one nds
σsol.sp. = π(r1 + r2 )2 . (3)
In the ase of olliding solid spheres, the ross-se tion equals the ¾ex luded
area¿ surrounding ea h target sphere. In the ase of moving target spheres
the number of target spheres en ountered on the path dx diers from Sndx.
PSfrag repla ements For the spheres moving toward ea h other this number in reases, in the
opposite ase it de reases. Therefore Eq. (3) should in lude orre tions
r1 + r2 depending on the relative velo ity.
If the s attering me hanism annot be redu ed to the ollision of solid
spheres the orresponding ross-se tion does not have a lear geometri
Fig. 2. Collision of solid spheres interpretation. However if the target parti les have low transparen y for
the parti lesproje tiles, Eq. (3) an still be used. The radii r1 and r2 in
this ase should be onsidered as ¾ee tive radii¿ whi h values an depend
Find the unit of measurement of σ . To do this onsider Eq. (1). The not only on the nature of olliding parti les, but on their energy as well.
unit of measurement of the left hand side is m−1 . The mole ular density The on ept of solid spheres is not appli able for ele tron ollisions. The
is measured in m−3 . Therefore the oe ient σ is measured in m2 . It is size of ele tron (if any) is negligible, so a tually it is a ollision of Coulomb
alled ross-se tion. elds of intera ting parti les. The ele tri eld of atom has a relatively sharp
boundary. Close to the nu leus it is very large. The nu leus eld de reases
The analysis leading to Eqs. (1) and (2) is independent of the type faster than r−2 be ause the harges of atomi ele trons ¾s reen¿ the eld.
of intera ting parti les, their velo ity, and the parti ular pro ess whi h Beyond atomi shells the nu leus harge is ompletely s reened, and the eld
de reases the number of parti les in the beam. These fa tors ae t the value is very small. The size of the region of spa e o upied by ele tri eld does
of σ rather than the general form of Eqs. (1) and (2). Therefore the ross- not dier mu h from the size of atom determined by other methods, so it
se tion hara terizes the dependen e of the s attering pro ess on the parti le an serve as atomi size as well.
type and intera tion. It should be lear from the above dis ussion that it is ne essary to
distinguish dierent ross-se tions of ele tron intera tion: the ross-se tion of
The on ept of ross-se tion be omes transparent in the ase of olliding elasti s attering σel (sigma-elasti ), the ross-se tion of inelasti intera tion
solid spheres. Figure 2 depi ts a beam of spheres of radius r1 passing solid σin (sigma-inelasti ), and the total ross-se tion σtot (sigma-total)2 :
immobile target spheres of radius r2 . Consider the ross-se tion of su h a
pro ess. First onsider only one target sphere. It is lear that all spheres σtot = σel + σin . (4)
whi h enters are lo ated on the traje tories passing at a distan e less than
r1 + r2 from the enter of the target sphere ollide with the target sphere. All these ross-se tions, σel , σin , and σtot depend on ele tron energy and
The area of the ¾ex luded region¿ equals π(r1 + r2 )2 . Now onsider the ase the type of target atoms. At low energies these ross-se tions have the same
of numerous target spheres. Let n be their on entration (the number of order of magnitude as a ross-se tional area of atom, but for ertain energies
spheres per one m3 ). There are Sndx target spheres in the layer whi h area they have sharp resonant maxima. Su h maxima are observed when ele tron
is S m2 and the width is dx. They blo k the way to in ident spheres on the 2 In the arguments leading to Eqs. (1) and (2) the parti les kno ked from the beam
area of π(r1 + r2 )2 Sndx. The part of the spheres kno ked from the beam, are all parti les whi h have undergone any intera tion: elasti , inelasti , or another.
energy approa hes an energy of atomi transition between the ground and
ex ited state, or when this energy be omes large enough to ionize atoms
moving toward the in ident beam. Using the s attering ross-se tion it is
possible to al ulate the mean free path of ele tron λ.
Equation (2) allows one to obtain the probability distribution of free
path. The probability that a parti le freely travels a distan e x equals
N (x)
F (x) = = e−σnx ,
N0
and the probability that free path is in the interval (x, x + dx), equals

P λ ∈ (x, x + dx) = F (x) − F (x + dx) = −F ′ (x)dx =
= σne−σnx dx = ρ(x) dx. À
Fun tion ρ(x) = σne−σnx is alled probability density. In our ase the PSfrag repla ements
m A
fun tion is the so- alled exponential distribution. R R
From the density ρ(x) one an nd the mean free mean: A
Z
∞ Z
∞ m A
1
λ= xρ(x) dx = x σne−σnx dx = . (5)
nσ Fig. 3. An experimental installation:
0 0
1) athode,
Both the mean free path and the ross-se tion depend on the type and 2) anode,
3) olle tor,
energy of olliding parti les, and on the details of ollision pro ess. 4) ammeter,
5,6) power supply units,
7,8) ammeters
Measurement. The prin ipal design of experimental installation for measuring
the ross-se tion of ele tron s attering on mer ury atoms is shown in Fig. 3.
The installation onsists of axially symmetri athode 1, anode 2, and
olle tor 3 lo ated in an eva uated ylinder (to 10−6 torr) ontaining liquid Ea h ollision an be both elasti and inelasti .
mer ury (∼0.5 m3 ). The installation is pla ed in a thermostat and immersed The more the number of possible intera tions, the
in a transformer oil. The saturation vapor pressure of mer ury is ontrolled 3
greater is the probability that ele tron does not
by oil temperature. 1 2
rea h the olle tor. It is lear that inelasti ollision
Ele trons a elerated in the gap between the athode and the internal removes ele tron from the ux that rea
PSfrag hes ements
repla the 2
anode grid freely pass in the anode avity to the external grid, the energy of olle tor. So, a de reasing olle tor urrent implies
ele trons remains onstant. In the region between the external anode grid emergen e of elasti and inelasti ollisions in the
and the olle tor the ele trons slow down and an rea h the olle tor if its anode spa e.
potential equals the athode potential.
Fig. 4. Ele tron path in
Ele tron path abruptly hanges its dire tion during elasti ollision with Now the method of measuring the total installation:
a mole ule of residual gas or mer ury atom, the length of the path in the ross-se tion of ele tron s attering on mer ury 1) athode
anode spa e in reases, and, onsequently, the probability to en ounter a 2) anode
atoms should be lear. In the experiment one 3) olle tor
mole ule on e more in reases as well (see Fig. (4). measures the dependen e of olle tor urrent Ic on
thermostat temperature T . Using Eq. (2) one nds: The ele tri ir uit depi ted in Fig. (3) is designed so that the anode
potential (and the olle tor potential) is determined with respe t to the
1 N0 kT N0 kT i0
σ= ln = ln = ln , (6) athode midpoint. Therefore in the drift spa e (i. e. between the anode grids)
nL Nc LP Nê LP iê the energy of ele trons is onned in e · (U ± V /2) where V is the potential
where i0 is the urrent emitted by athode, ic -is the olle tor urrent, k is dieren e between the edges of the emitting se tion of the athode.
Boltzmann's onstant, T is the temperature of mer ury vapor, and P = Now onsider Fig. 5. An ele tron in the drift spa e ollides with an atom
= nkT is the pressure of mer ury vapor. at point C, hanges its dire tion of motion and travels, say, to point D.
The obtained equation would be rigorous if in the absen e of mer ury If its energy W = m(v cos α)2 /2 turns out to be greater or equal to the
atoms all ele trons emitted by the athode rea hed the olle tor. A tually potential dieren e between the anode and olle tor, i. e. eU , the ele tron
this is not what happens sin e a signi ant part of ele trons ends up on the rea hes the olle tor surfa e and therefore the ollision at point C is not
anode. Let the part of ele trons whi h rea h the olle tor in the absen e of dete ted.
mer ury atoms be κ . A ording to the above argument one an write Eq. (6) Thus, the maximum energy whi h ele tron an have equals e(U + V /2).
as The ondition of its dete tion (the ele tron does no rea h the dete tor) is
kT i0
σ= ln κ , (7)
LP ic m(v sin α)2 eV
> . (9)
when e 2 2
kT kT i0
P = ln κ + ln . (8) If eV /2 > m(v sin α)2 /2 the ele trons with maximum energy rea h the
Lσ Lσ ic
olle tor and therefore do not arry information about the ollision with
One an see that dependen e of pressure P on ln ii0c must be linear. The
atom.
slope of the straight line allows one to determine the s attering ross-se tion
Let us draw the dashed line through the points D and C, and draw
σ = σtot . The rst term in Eq. (8) is responsible for ele tron absorbtion in
the perpendi ular from the point 1 (the athode) to this line. Let the
the absen e of gas. This term only shifts the line without hanging its slope.
perpendi ular length be r. Now let us onne t the point D and the athode
Cross-se tions are usually measured in m2 . Therefore when plotting the
with a straight line. The length of this line is the olle tor radius R. It is
graph using Eq. (4) it is onvenient to employ a physi al system of units.
lear from the onstru ted triangle that R sin α = r and the normal and
Currents i0 and ic an be measured in any system sin e they enter the
tangent velo ity omponents of ele tron ollided with atom at the point C
equation via the ratio. Pressure in va uum installation is usually measured
are v cos α and v sin α. Substituting sin α = r/R into Eq. (9) one obtains
in torr (mm of Hg ). It is useful to remember that 1 torr = 133 Pa.
repla ements
Estimation of numeri al value of L. An mv 2 r 2
· >
eV
. (10)
3 ele tron emitted by the athode travels along a 2 R 2
2 radius with energy W = mv 2 /2 where m is ele tron
D Sin e
mass and v is ele tron velo ity. The latter an 2
mvmax
α R 1 2 be found from the relation mv 2 /2 = eU , where = e(U + V /2), (11)
2
C e is ele tron harge and U is the anode potential
r then
relative to that of the athode if their surfa es r
V
are equipotential. For the sake of onstru tion r=R . (12)
2U + V
simpli ity and durability the athode is made of
a straight tungsten wire dire tly heated by ele tri Thus the installation dete ts a ollision whi h o urs at a distan e greater
Fig. 5. Diagram for urrent. Tungsten is both hemi ally and physi ally than r from the athode. Therefore, the value of L is given by
al ulating energy and
momentum of ele tron immune to mer ury vapor at room temperature " r #
between ele trodes and at the temperature of ele tron emission. This V
L=R−r =R 1− . (13)
provides the installation longevity. 2U + V
For our installation (R = 2 m, U = 5 V, V = 2 V) one obtains L ≈ 1.2 m. temperature (the thermostat and its mixer are turned on, the heater
is turned o). Due to various fa tors the urrent i0 does not remain
Laboratory setup. The experimental installation (the ross-se tion along
onstant but varies slowly. The ratio i0 /ic an also hange be ause of that.
a diameter) is shown in Fig. 3. Filament athode 1 made of tungsten is
Therefore after turning on the installation, while it is being heated at room
lo ated along the devi e. Anode 2 is formed by two ele tri ally onne ted
temperature, arry out auxiliary measurements, i. e. re ord 1015 of the
oaxial ylinder grids whi h top and bottom are losed by lids. Colle tor 3
values of i0 and ic and plot the time dependen e of ln(i0 /ic ) = f (i0 ).
has a ylindri shape and is made of metal foil. The athode, anode, and
Determine the deviation of ln(i0 /ic ) from its average value. The deviation
olle tor are en losed in a glass ontainer whi h has about 0.5 m3 of liquid
an be used to estimate the error of the results.
mer ury inside. The ontainer is eva uated and sealed.
After initial heating is over pro eed to the main experiment. If the
All potentials in the installation are measured with respe t to the
range of variation of i0 obtained in the experiment is less than the
potential of athode midpoint. This potential is reprodu ed at the point
range dete ted in auxiliary measurements, one should take the value
A by divider R − R. The athode is heated by the urrent supplied by
orresponding to the range of variation i0 obtained in the experiment as the
power supply 5 and measured by the meter 4. Power supply unit 6 serves to
experimental error rather than the maximum deviation ln(i0 /ic ) obtained
maintain the anode potential. The rst terminal of the unit is onne ted in
in auxiliary measurements. This error should be indi ated on points of the
series with ammeter 7 to the point A and the se ond terminal is onne ted
plot ln(i0 /ic ) = f (i0 ).
to the anode. The olle tor is onne ted in series with ammeter 8 to the
Re ord the dependen e of anode (i0 ) and olle tor (ic ) urrents on
point A; the ammeter measures the olle tor urrent.
temperature T of the thermostat working liquid from 20 to 50 ◦ C with
Now it should be lear that the total s attering ross-se tion of ele trons
5 ◦ C in rement both for in reasing and de reasing temperature. During the
on mer ury atoms is determined from the dependen e of olle tor urrent
experiment the working liquid must be ontinuously mixed and the athode
on pressure of mer ury vapor. In our devi e this dependen e is reliably
should be maintained in operation mode, i. e. its heating must be on during
measured at pressures from 10−3 to 10−2 torr, whi h orresponds to
in reasing and de reasing thermostat temperature (intera tion of mer ury
thermostat temperature from 20 to 50 ◦ C.
vapors with tungsten is negligible).
The lament urrent is set so that the reading of mi roammeter 8 is
Using the table
∼1 µA (in the range of 1 µA). The voltage of power supply unit 6 dete ted
by voltmeter 9 (on the anode) equals 5 V. During the experiment the T ◦C 20 25 30 35 40 45 50 55 60
value of the anode voltage and the lament urrent should not be hanged P, 10
−3
torr 1.3 1.8 2.78 4.1 6.1 8.8 13.4 18.9 26.5
signi antly in order to onserve the onguration of ele tri eld in the
installation and, onsequently, the value of oe ient κ in Eq. (7). onvert temperature into pressure of saturated mer ury vapor and treat the
To vary the temperature the installation is pla ed in the thermostat lled results obtained using Eq. (8).
by oil. The oil is ne essary to prevent a leakage between ele tri onta ts. Draw the best t line in the limits of measurement errors. Using the
The thermostat ontains an ele tri heater to heat the working liquid formula
and a oil to ool the liquid by running tap water. On the ontrol onsole kT d ln(i0 /ic )
σ= ·
of the thermostat there is a ommon slide swit h and a toggle swit h for L dP
turning on and o the system of mixing the working liquid. Temperature determine the intera tion ross-se tion σ . (Set the value of L in Eq. (8)
of the working liquid is measured by a thermometer with 1 ◦ C graduations. to 1 m.). Using this value of σ and the formula λ = 1/(nσ) (where n =
The temperature at whi h the heater is turned o is set by a mer ury onta t = P/(kT )) valid for single ele tronatom ollision estimate temperature Tx
thermometer with 2 ◦ C graduations. A required temperature value is set by for λ = L, i. e. when the ele tron free path equals the devi e parameter
rotating a magneti head on the onta t thermometer. L. For temperature T > Tx an ele tron undergoes multiple ollisions. The
installation is based on the theory valid for the free path λ > L, i. e. for
LABORATORY ASSIGNMENT the ase of single ollision. For this reason the results obtained for T > Tx
Turn on the installation, set the operation values of urrents i0 and ic should be ex luded from further pro essing. Restri ting the plot to T < Tx
and heat the installation for 2030 minutes without hanging the installation draw the best t line for this part and using its slope obtain the nal value
of σ . Using this value nd λ and estimate the diameter of mer ury atoms. by denition, the equilibrium pressure in the bulb is the saturated vapor
Compare the result with the estimate based on the value of density of liquid pressure (at a given temperature).
mer ury (13.6 g/ m3 ). The appli ation of this te hnique an fa e signi ant di ulties, espe ially
if we deal with refra tory metals. The problem is that we an obtain the
Remark. For the sake of rigor one should plot the graph f (P/T ) rather than orre t value of the saturated vapor pressure only if the studied substan e,
f (P ). However ∆T ≪ T0 (T0 is the initial room temperature in kelvins), so
its saturated vapor, and the bulb have the same temperature. To a omplish
it su es to substitute T = T0 + (∆T /2) and then the dependen e be omes
this we have to hoose the material of the bulb with the saturated vapor
f (P ).
pressure mu h less than that of the studied substan e. This ondition is
Questions di ult or even impossible to meet if we deal with refra tory metals. In
addition, it is non-trivial to measure the pressures at several thousand
1. What is s attering ross-se tion? What ross-se tion is alled elasti , inelasti ?
degrees.
2. How are ross-se tion and free path onne ted? Derive Eq. (5).
The determination of the saturated vapor pressure of a metal is based
3. What law determines the dependen e of the pressure of saturated vapor of a liquid
on the following idea. Consider a substan e in thermodynami equilibrium
on temperature?
with its vapor. The number of parti les leaving a surfa e per se ond equals
4. Why should the installation be immersed in liquid ompletely, i. e. with all its
proje ted parts?
the number of parti les in ident on the surfa e from the vapor. From the
kineti theory of gases we know that the number of parti les N in ident on
Literature unit area of a at surfa e per se ond equals
1. Sivuhin D.V. General ourse of physi s. V. II. Thermodynami s and mole ular
1
physi s. M.: S ien e, 1975. 86, 87, 88, 114. N= nv, (1)
4
òîâàÿ è ñòàòèñòè÷åñêàÿ èçèêà. Ì.: Ôèçìàòëèò, 2001. ×. 5. ë. 1, 1.3. where n is the on entration of vapor mole ules and v is the average velo ity
3. Astakhov A.V. Course of physi s. I. M.: S ien e, 1977. 5.2, 9.1. of the mole ules. Equation (1) allows one to determine n and, hen e, the
4. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001. vapor density if N and v are known. The velo ity an be easily al ulated at
Ñ. 78. a given temperature, so the problem is redu ed to measuring N . However,
5. Ñáîðíèê çàäà÷ ïî îáùåìó êóðñó èçèêè / Ïîä ðåä. Â.À. Îâ÷èíêèíà. ×. 1. this is not very simple.
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 226227. The destiny of mole ules in ident from the vapor on the solid surfa e is
dierent. A fra tion of mole ules (we denote it by N1 ) re oil with the same
energy, while the other fra tion N2 settles on the surfa e. The quantity N
2.3.5. Measurement of saturated vapor pressure in Eq. (1) is the net number of mole ules:
of a refra tory metal N = N1 + N2 . (2)
Purpose of the lab: 1) to measure the mass of evaporated metal; 2) to The number of mole ules evaporated from the surfa e in thermodyanmi
al ulate the vaporization temperature by equating radiation losses and equilibrium is N2 .
supplied ele tri power; 3) to determine the saturated vapor pressure If we remove the evaporated mole ules by va uum pump the ow of
using the vaporization temperature and the duration of vaporization of parti les in ident on the surfa e will vanish. The ree ted ow N1 will vanish
the measured mass of metal.
as well. The number of mole ules es aping to the gaseous phase will be equal
Tools and instruments: a va uum installation; a stopwat h; and a to N2 , it an be determined by measuring the de rease of the mass of solid. If
tantalum wire with diameter d = 0.1 mm. the relation between N and N2 is known, the latter an be used to al ulate
the saturated vapor pressure. If the relation is unknown the value of N2
The dire t measurement of a saturated vapor pressure is performed as an be used as well, but in this ase the result will be a urate within the
follows: a liquid or solid under study is pla ed into a losed eva uated bulb; relative dieren e between N and N2 . The ratio N2 /N is referred to as
evaporation fa tor, it an vary from 0.04 (water) to 1 ( arbon tetra hloride while at onstant urrent I
and many metals). This ratio is lose to 1 for refra tory metals, parti ularly 1/4 2 1/4 1/4
UI I R 1
for tantalum. T ∼ ∼ ∼ ∼ r−3/4 ∼ M −3/8 .
In what follows we do not distinguish between N2 and N . Let us express S S SS1
the mass of an evaporated substan e via the pressure of its saturated Here r is the wire radius.
vapor. Introdu ing the following notations: ∆M for the mass of evaporated Hen e we see that onstant voltage should be maintained during the
substan e, m for the mass of a single atom, t for time, S for the surfa e area, experiment.
and P for the vapor pressure, we write Laboratory setup. The experiment is made using a high-va uum installation
r
t t P m shown in Fig. 1. It onsists of a high-va uum hamber HC and two pumps:
∆M = N mtS = nvmS = vmS = P tS . (3)
4 4 kT 2πkT me hani al ba king pump BP and diusion pump DP made of metal. The
In this experiment the saturated vapor pressure of tantalum is measured ba king pump is powered by ele tri motor, it allows one to obtain pressures
at several thousand kelvin. At this temperature about 510% of the 10−2 10−3 torr.
substan e under study is evaporated for half an hour. In the experiment The diusion pump is used to obtain high va uum. The working
a thin ele tri ally heated tantalum wire is used; its temperature an be substan e of this pump is a diusion oil with saturated vapor pressure
determined via the equation of balan e between the power of Joule heating about 10−9 torr at room temperature. The oil is heated by ele tri oil
and thermal radiation: EC and vaporizes intensely. The vapor goes up the tube along the pump
W = U I = C1 σT 4 S, (4) axis and ows out through the nozzles dire ting the steam jet along the
pump walls. The steam aptures the gas mole ules in the top se tion of
where U is the voltage drop a ross the wire, I is the urrent, σ is the the diusive pump and drags them to the bottom se tion where they are
Stefan-Boltzmann onstant (σ = 5.67 · 10−8 J/m2 ·K4 ), and C1 is the radiant removed by the ba king pump. The walls of the diusive pump are ooled
emittan e fa tor (C1 equals unity for a bla k body and is less than unity by water, so the oil vapors ondense on the walls. The oil owing down along
for any real radiating obje t. We will see that the nal equation ontains
√ the walls returns to the heating hamber. The steam pressure is about 0.1
8
C1 and the value of the emittan e fa tor does not signi antly ae t the torr; for this reason the diusion pump is operable only if the pressure in
result. For tantalum C1 = 0.55). The loss of heat through the wire ends the installation does not ex eed this value. The preliminary eva uation is
and the energy arried out by the vaporized atoms an be negle ted at done by the ba king pump. Under proper air-proong the ultimate va uum
su h high temperatures (the students are re ommended to perform relevant reated by the diusion pump rea hes 10−6 torr. The ba king pump should
estimations). Eliminating the temperature from Eqs. (3) and (4) we nd: operate ontinuously on e the diusion pump is on.
r r
∆M 2πk 8 U I The pumps are onne ted by a pipe with valve V1. The valve V2 serves
P = . (5) for pre-eva uation of HC (without using the DP), the valve V3 onne tes
tS m 0.55σS
HC and BP with the atmosphere. The valves V1, V2, and V3 are losed
This is the nal equation.
by rotating their handles lo kwise and opened by rotating them ounter-
Let us now examine how the wire evaporation ae ts the results of
lo kwise.
experiment. During evaporation the surfa e area of the wire S de reases
The high va uum hamber and the diusion pump are separated by the
while its resistan e R = ρl/S1 in reases (here ρ is the resistivity, S1 is the
gate valve manipulated by handwheel H. The gate valve has a large ross
ross se tion, and l is the wire length). Both fa tors lead to a hange of the
se tion (in our installation its diameter is 10 m) thereby providing high
wire temperature. Now let us show that the result of the experiment is less
speed of HC eva uation. The ultimate pressure of the HC is determined
ae ted by the variation of mass if we maintain a onstant voltage a ross
(provided there are no leaks and gas sour es inside the hamber) by the
the wire (rather than maintaining a onstant urrent). By inspe ting Eq. (4)
saturated vapor pressure of diusion oil, whi h, in turn, depends on the oil
one an see that at onstant voltage U
temperature. To redu e the oil temperature a trap is mounted between the
1/4 2 1/4 2 1/4
UI U U S1 diusion pump and the gate valve. The trap is a metal disk with openings
T ∼ ∼ ∼ ∼ r1/4 ∼ M 1/8 , ooled by tap water.
S RS S
opened). During the pre-eva uation the diusion pump operates without any
T I assistan e of the ba king pump, su h a regime is allowed only for a short
period of time (∼10 minutes). Se ond, after the pre-eva uation is omplete,
separ. the hamber must be isolated from the ba king pump (the valve V2 losed),
transf.
autotransformer
and the ba king pump is again onne ted to the diusion pump using the
valve V2. Then the gate valve between HC and diusion pump is opened.
Thermo ouple va uum gauges T1 and T2 and ionization va uum gauge I
RF are used to measure pressure in the installation. A thermo ouple gauge
is a glass bulb with a ni kel wire heated by a dire t urrent. The wire
temperature is measured by a thermo ouple atta hed to its midpoint.
HC At a given urrent the wire temperature is determined by the thermal
ondu tivity of the environment. The heat released by the wire to the
H surrounding gas per se ond depends on gas pressure (providing the pressure
V is in the operating range of the gauge: from 1 to 10−3 torr). The gauges VT-
water 2 and VIT-2 onne ted to the lamp T1 serve as indi ators of thermo ouple
DP readings.
The ionization va uum gauge is a tube with three oaxial ele trodes:
water discharge athode, anode, and olle tor. The heated athode emits ele trons whi h
are arried by the ele tri eld of the anode. The anode is a sparse heli al
wire, so the ele trons freely pass between its turns. After passing through
EC the anode the ele trons are de elerated by the olle tor eld and return to
T
the athode, and so on. On their way the ele trons ionize gas mole ules,
V1 and ions generated between the anode and the olle tor are attra ted by the
V2 latter and ontribute to its urrent.
The ion urrent in the olle tor ir uit is proportional to the gas density
V3 and, hen e, to its pressure. The ionization probability depends on the gas
in the bulb (and in the eva uated volume as well). The alibration of the
va uum gauge is orre t if the residual gas is air.
atmosphere gas exhaust The heated athode of the ionization gauge fuses if the gas pressure
ex eeds 1 · 10−3 torr. For this reason the ionization va uum gauge an be
BP turned on only if the thermo ouple gauge readings are below 10−3 torr.
During measurements the wire of the ionization gauge is intensely heated,
Fig. 1. Experimental setup
whi h in reases the temperature of its surroundings. Due to this fa t both
the ele trodes and the bulb walls an desorb the gases adsorbed previously.
The removable ange RF allows one to gain a ess to the high- The emitted gases hange the pressure in the bulb whi h results in in orre t
va uum hamber. Before opening the hamber one should onne t it to readings. To prevent this the ionization va uum gauge should be warmed
the atmosphere using the valve V3. One an open the HC even during up (degassed) for 1015 minutes prior to measurements.
operation of the diusion pump, however, the gate valve and the valve V2 The removable ange RF is atta hed to the HC with bolts. A ring made
should be tightly losed during the opening. After that the eva uation is of va uum rubber is interlaid between the ange and the hamber walls to
done in two steps. First, the hamber is pre-eva uated by the ba king pump maintain the air-tightness of the setup. The ele trodes are mounted on the
(the gate valve and the valves V1, V3 should be losed and the valve V2 ange and ele tri ally isolated from it. The s rews used as the wire supports
are lo ated on the butt ends of the ele trodes both on the inner (inside the operation one an resume eva uation of HC (after losing V1 and opening
hamber) and the outer sides. V2). If the ultimate va uum in the HC is above 10−2 torr one should all
The external ele tri ir uit ontains an ammeter, a voltmeter, a the instru tor and eliminate the leaks under his supervision.
transformer, and an autotransformer. 7. Pro eed to the high-va uum pumping. Close V2, open V1 and the gate valve.
Running water for ooling the diusion pump is fed through the valve Wat h the readings of T1 : its pointer should qui kly rea h the end of the
V. To tra k the water dis harge a ow meter is mounted in the downow s ale.
pipe. 8. Conne t the power sour e to the lamp terminals on the ange. Using the
values of the diameter and length of the wire al ulate its surfa e area and
LABORATORY ASSIGNMENT using the equation W = 0.55 σST 4 , estimate the power required to heat the
1. Make sure that the diusion pump is ooled. Open the valve V3 whi h wire up to the temperature T = 2600 K.
onne ts the va uum hamber to the atmosphere. 9. After the pressure in HC falls down to ∼10−4 torr (see the readings of T1 ),
2. Unbolt the ange RF. To prevent the ange from skewing do the following: plug the autotransformer in an outlet. In rease the urrent through the wire
ease o one bolt, then ease o the opposite one (rather than its neighbor). (∼1.6 A) until the power al ulated above is a hieved. Write down the values
When the ange is removed inspe t the gate valve inside the hamber. Open of the urrent and the voltage. Heat the wire for several se onds to remove
and lose the gate valve by rotating the handwheel. Whi h position of the water and fat ontaminants from its surfa e.
hanwheel orresponds to the open valve and whi h to the losed one? Che k 10. Close the gate valve se urely and onne t the HC to the atmosphere (open
whether your observations agree with the handwheel engraving. V3). Remove RF, arefully take the spiral o and weigh it on a s ale. Using
3. Dis onne t the ba king pump from the atmosphere by losing the valves the mass M , the wire length l and the density of tantalum
p D = 16.6 g/ m ,
3
V3 and V2. Conne t the ba king and diusion pumps by opening the valve al ulate the wire radius and the surfa e area S , S = 2 πM l/D.
V1. Start the ba king pump and observe the readings of the gauge T2 . 11. Fix the helix on the ange, pla e the ange ba k to its position and tighten
Start the diusion pump after the pressure falls below 0.1 torr. To do this the s rews.
open the fau et supplying the water to ool the pump and after that swit h 12. Dis onne t HC from the atmosphere and pre-eva uate it with the ba king
on the heater. Starting the heater is prohibited unless the water supply is pump (through the valve V2) down to several per ent of torr (2025 s ale
on; if the water supply failed during the operation of the diusion pump graduations of PMT-2). Conne t the BP to the DP after that.
the heating should be immediately swit hed o. The heater warms up for
13. Start the diusion pumping by opening the gate valve. After the high
several minutes, during this time you an prepare the wire sample.
va uum (∼10−4 torr) is rea hed, swit h on the PMI-2 lamp and measure
4. Cut a pie e of tantalum wire 15-20 m long (its diameter is d = 0.1 mm). the pressure inside the hamber. Start the measurements as soon as the
Wind the wire about a rod 15 mm in diameter to make a helix.
pressure falls down to 10−4 10−5 torr.
5. Atta h the helix to the ele trodes on the side fa ing the va uum hamber.
14. Conne t the wire to the power sour e and, using the data obtained before, set
To avoid wire sagging during the heating suspend the midpoint of the helix
the urrent and the voltage orresponding to the wire temperature of 2500
on the wolfram upright mounted on the ange between the ele trodes.
2600 ◦ C. Start the stopwat h. Maintain the onstant voltage a ross the wire
6. Set the ange in pla e and bolt it trying to avoid a skew. Tighten the s rews during the experiment. The evaporation rate an be estimated by observing
on the bolts manually without using wren hes or pliers. Close the valve V1, the time dependen e of the urrent and using the following equations
open V2, and start pre-eva uating the hamber (wat h the readings of T1
and remember that DP an operate without BP no longer than 10 min). U U dM dI
One should also wat h the readings of T2 . It ould happen that va uum in I= = S, M = DLS1 , hen e = .
R ρl M I
the HC ( ontrolled with T1 ) in reases slowly or does not in rease at all. This
usually o urs if the ange is not properly sealed or the valve V3 is not tightly The urrent de rement of 5% is su ient to determine the saturated vapor
losed. Va uum in DP ( ontrolled with T2 ) an also gradually de rease; if pressure.
the readings of T2 fall below 0.1 torr one should lose V2, open V1 and 15. Time dependen e of urrent allows one to estimate the evaporation rate only
eva uate the volume of DP below ∼10−2 torr. Only after performing this qualitatively. The problem is that the wire resistivity ρ depends on the wire
166 MOLECULAR PHENOMENA
rystalline stru ture whi h an be signi antly altered during heating. This Chapter IV
pro ess an lead to un ontrolled variations of the urrent; for this reason the
wire should be weighed on a s ale after the evaporation. To do this swit h
o the ionization va uum gauge, lose the gate valve, open the HC to the
PHASE TRANSITIONS
atmosphere (keep the volume of DP eva uated), remove the ange with the
helix, arefully remove the wire and weigh it. One should not swit h on the
PMI-2 lamp in the subsequent experiments to avoid its fusion, moreover,
the ultimate va uum is known from the previous experiments, so repeated
usage of the ionization gauge will not give any additional information. The
T1 and T2 gauges are su ient to ontrol the va uum.
16. Fix the helix on the ange, set the ange in pla e and repeat the
measurements des ribed in pp. 1215 (without swit hing on PMI-2 lamp)
at the voltage of 510% higher (i.e. at a higher wire temperature). Repeat Phases of matter are homogeneous regions of a substan e separated by
the measurements in reasing the voltage by 510% ea h time until the wire boundaries and dierent in their physi al properties. Dierent phases are
fuses. the aggregated states of matter: gaseous, liquid, and solid. A hunk of i e
17. As soon as the measurements are ompleted swit h o T1 (VIT-1), lose the oating in water provides an example of a two-phase system whi h in ludes
gate valve and unplug the heater of DP. Open the HC to the atmosphere, solid and liquid states. Water and vapor in a kettle are examples of liquid
remove the helix and weigh it on a s ale. The manometer T2 should keep and gaseous phases.
operating to ontrol the va uum in the diusion pump during its ooling. The on ept of phase is more general than the on ept of aggregate
The manometer should be swit hed o only after utting water o . state. Dierent phases an exist in the same aggregate state. Usually a solid
18. Cut water o and swit h o the ba king pump in 3040 minutes after state is omposed of several dierent phases with distin t rystal latti es. To
swit hing o the DP (if you do not have enough time KINDLY ask be spe i , onsider some examples: graphite and diamond; sulphur whi h
the laboratory assistant to do this). Conne t the volume of BP to the has rhombi rystals (regular yellow sulphur) and mono lini sulphur; white
atmosphere; the DP should remain eva uated. Swit h o the manometer tin with tetragonal stru ture whi h is stable at atmospheri pressure and
T2 . temperature above 18 ◦ C and gray tin whi h is stable at lower temperatures.
19. Cal ulate the wire temperature and pressure of the saturated vapor at The equilibrium between dierent phases requires both me hani al and
sele ted voltages. Plot the vapor pressure vs. the wire temperature. Evaluate thermal equilibrium, i.e. their temperatures and pressures must be the same.
the pressure in torr (mm Hg). Yet, this is not enough sin e the mass of one phase an hange at the expense
of another one. A stationary state with onstant number of mole ules in
Literature dierent phases an be realized only if ertain ondition between pressure
1. Course of general physi s. P. II. M.: 1975. 73, 75, 114.
Sivu hin D.V. and temperature is satised. The orresponding urve on P − T diagram
2. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976. is alled oexisten e urve. Let us prove that the urve an be found by
ë. 4, 7. equating spe i Gibbs energies of the phases.
3. Êîðîòêîâ Ï.Ô. Ìîëåêóëÿðíàÿ èçèêà è òåðìîäèíàìèêà. Ì.: ÌÔÒÈ, 2001. The Gibbs energy Φ is a fun tion of the system state, it is dened as
Ñ. 7880.
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 226227.
Φ = U + P V − T S. (4.1)
A ording to the rst two laws of thermodynami s the dierentials of

thermodynami quantities are related as (see Eq. (1.8)):
dU = T dS − P dV. (4.2)
168 PHASE TRANSITIONS Chapter IV 169
Using Eq. (4.1) we nd: Equation (4.8) is alled Clausius-

Clapeyron equation.
dΦ = −SdT + V dP. (4.3)
This equation is used in lab 2.4.1
Therefore the Gibbs energy Φ(P, T ) remains onstant in a thermodynami to determine the vaporization heat
system omposed of one or several phases providing the temperature and of a liquid. By measuring dP/dT , T ,
pressure of the system do not hange. v1 , and v2 one an al ulate q using
uid
Consider a system omposed of the phases 1 and 2 whi h masses are Eq. (4.8). To this end the equation
liq
m1 and m2 . Let the spe i Gibbs energies of ea h phase be ϕ1 (P, T ) and should be simplied and transformed.
ϕ2 (P, T ). Then At temperatures whi h are not
Φ = m1 ϕ1 + m2 ϕ2 . (4.4) lose to the riti al temperature of solid body gas
the studied liquid, the spe i volume
During a phase transition the quantities ϕ1 and ϕ2 do not hange sin e P
of vapor greatly ex eeds that one of
and T are onstant, only the masses m1 and m2 vary. Then equation (4.4)
the liquid, so v1 an be negle ted. In
gives ϕ1 dm1 +ϕ2 dm2 = 0. Sin e the net mass does not hange, dm1 +dm2 =
addition, the saturated vapor an be Fig. 4.1. Phase diagram. A is triple point,
= 0. Now it is obvious that two phases are in equilibrium providing their
des ribed by the equation of state of K is riti al point
spe i Gibbs energies are equal:
ideal gas:
ϕ1 (P, T ) = ϕ2 (P, T ). (4.5) v2 =
RT
. (4.9)
µP
Let us apply Eq. (4.3) to ϕ1 and ϕ2 : Substituting Eq. (4.9) into (4.8) and negle ting v1 one nds:
dϕ1 = −s1 dT + v1 dP, dϕ2 = −s2 dT + v2 dP. (4.6) RT 2 dP R d ln P
q= =− . (4.10)
It follows from Eq. (4.5) that dϕ1 = dϕ2 and using Eqs. (4.6) one obtains: µP dT µ d(1/T )
dP
=
s2 − s1
. (4.7) This formula is onvenient in treating the experimental results.
dT v2 − v1
Here s1 , v1 , s2 , v2 are spe i entropies and volumes of ea h phase. Let us Figure 4.1 shows the lines on P −T diagram where two phases an oexist.
nd the dieren e of spe i entropies using the fa t that phase transition The lines are also the boundaries separating solid, liquid, and gaseous phases.
o urs at onstant temperature. Vaporization of a unit mass requires the At the triple point A, where three lines interse t, all three phases an oexist
spe i heat of vaporization q . Then a ording to the denition (1.7) at simultaneously.
onstant temperature Consider melting urves. These urves go steeply up be ause the
q dieren e between spe i volumes of liquid and solid phases is small. The
s2 − s1 = .
T urves an be tra ed up to very large pressures, in theory - up to innity.
Substituting it into Eq. (4.7) we obtain Most of substan es in rease their volume when melting be ause their
rystal latti e be omes disordered. Therefore the melting urve has a positive
dP q
= . (4.8) slope (N2 , ÑÎ2 , Cu, Fe, Al, NaCl). However the melting urve slope an be
dT T (v2 − v1 )
negative if the spe i volume of solid phase ex eeds the liquid one, e.g. for
Here q is the spe i heat of phase transition from state 1 to state 2. This i e, bismuth, and gallium.
quantity is positive for vaporization pro ess and negative for ondensation. Vaporization urve of liquid has a signi antly smaller slope sin e spe i
Noti e that spe i volumes are ex hanged in a reverse pro ess, so that volume of gas is usually large ompared to spe i volume of liquid and solid.
the slope of the line of phase boundary is the same for vaporization and Unlike a melting urve a vaporization urve terminates at the riti al point K
ondensation. (for water Tc = 647 Ê (374 ◦ C), Pc = 22 MPa (218 atm)). By getting around
170 PHASE TRANSITIONS 2.4.1 171
this point, i.e. hanging the pressure and temperature in a spe i way one surfa e form a vapor. In order to es ape from the surfa e the mole ules
an ontinuously transform liquid to gas and vi e versa. Stri tly speaking must over ome intermole ular for es. Besides, during evaporation a work is
liquid and gaseous states are dened only on the vaporization urve where done against the external pressure P sin e the spe i volume of liquid is
they are in equilibrium and have dierent densities. less than that of the vapor. Not all mole ules are able to es ape from the
As it follows from the phase liquid but those with su ient kineti energy. Therefore evaporation results
P, atm diagram, ompressing a gas in order in ooling the liquid be ause of depletion of its sto k of rapid mole ules. In
to liquefy it is not enough, the gas order to maintain onstant temperature during evaporation the liquid must
40 Solid must be ooled below the riti al be heated. The amount of heat required for isothermal vaporization of one
body temperature. mole of liquid at the pressure equal to the saturated pressure of the liquid
30 At pressures less that at the triple vapor is alled the molar heat of vaporization.
point a solid an be vaporized evading The heat of vaporization of a liquid an be measured dire tly with the
20 the liquid phase. This pro ess is aid of a alorimeter. However the a ura y of this method is low be ause of
Liquid alled sublimation. (For example, wet un ontrollable heat losses whi h are di ult to redu e. In this experiment
10
К
laundry left outside on a frosty day we use the indire t method based on the Clausius-Clapeyron relation: (4.8):
Gas freezes and some time later dries.)
Near the triple point the heat dP L
0 1 2 3 4 5 T, К = . (1)
of sublimation qs equals the sum dT T (V2 − V1 )
Fig. 4.2. Phase diagram of 4 Íå of melting heat qm and vaporization
heat qv , therefore the sublimation Here P is the pressure of the saturated vapor of liquid at the absolute
urve is steeper than the vaporization temperature T , L is the heat of vaporization, V2 is the vapor volume, and
urve: V1 is the volume of liquid. Measuring dP/dT , T , V2 , and V1 one an al ulate
(dP/dT )s−g qs (vg − vl ) qs qm L. The quantities L, V2 , and V1 in Eq. (1) refer to the same amount of matter,
= ≈ =1+ .
(dP/dT )l−g qv (vg − vs ) qv qv we hoose it to be one mole.
In our installation the measurements are done at pressures below the
At temperatures lose to absolute zero all substan es be ome solid,
atmospheri pressure. This simplies the pro edure signi antly.
ex ept helium 3 Íå and 4 Íå whi h remain liquid at low pressure be ause
of quantum ee ts. 4 Íå solidies only at pressures ex eeding 25 atm. The The table lists the following parameters of several liquids: the temperature
phase diagram of 4 Íå is shown in Fig. 4.2, this substan e has the riti al at whi h the pressure of the saturated vapor equals the atmospheri pressure,
point and no triple point! the spe i volumes V2 and V1 , and the parameters a and b of the Van der
Waals equation.
b, a, a/V22 ,
2.4.1. Measurement of vaporization heat of liquid Tboil , V1 , V2 ,
Substan e 10−6
10
−3
10
−6
Purpose of the lab: 1) to measure the pressure of saturated vapor of Ê m3

mol
m3
mol
m3
mol
P a·m6
mol2
kPa
a liquid at various temperatures; 2) to determine vaporization heat from Water 373 18 31 26 0.4 0.42
the results using the Clausius-Clapeyron relation. CCl4 350 97 29 126 1.95 2.3
Diethyl ether 307 104 25 137 1.8 2.9
Tools and instruments: a thermostat; a sealed ontainer lled with the
liquid under study; and a mi ros ope. Ethanol 351 58 29 84 1.2 1.4
Evaporation is a pro ess of matter transition from liquid to gaseous state. One an see that V1 is less than 0.5% of V2 , so given the a ura y of our
Evaporation takes pla e on a free surfa e of a liquid. Mole ules leaving the experiment the volume V1 in Eq. (1) an be negle ted.
172 PHASE TRANSITIONS 2.4.1 173
In what follows the volume V2 is denoted by V . The volume V enters

the Van der Waals equation:
a
P + 2 (V − b) = RT. (2)
V
The table shows that b and V1 are of the same order, so the parameter
b in the Van der Waals equation should be negle ted. Negle ting the term
a/V 2 ( ompared to P ) introdu es the error less than 3%. The error be omes
even less at the pressures below the atmospheri pressure, so any dieren e
between the Van der Waals equation for saturated vapor and the ideal gas
law be omes negligible. Thus
RT
V = . (3)
P
Fig. 2. Setup for measuring heat of vaporization
Substituting Eq. (3) into Eq. (1), dis arding V1 , and solving the equation
for L we obtain
RT 2 dP d(ln P ) Figure 2 shows a detailed diagram of a similar setup whi h employs a
L= = −R . (4) modern thermostat. The setup in ludes thermostat A, installation B, and
P dT d(1/T )
a mi ros ope C. Figure 2 of the lab 2.2.6 shows a thermostat photo. The
This formula is nal. A similar formula for the spe i heat of vaporization
detailed operation guide an be also found in the lab.
an be found on p. 169.
The installation B is a vessel 12 lled with water. A sealed ontainer 13
In our experiment the temperature of
with the studied liquid 14 is pla ed inside the vessel. Before the ontainer
liquid is measured by a thermometer, the
water
was sealed it had been eva uated, so there is only the saturated vapor left
cold
air
pressure is determined by a manometer, and

above the liquid. The vapor pressure is determined by means of the mer ury
the quantities dP/dT or d(ln P )/d(1/T ) are
manometer 15 onne ted with the ontainer 13. The pressure is measured
al ulated as the slopes of tangents to the
as the dieren e of the position of mi ros ope 16 su essively trained on the
urve P (T ) or to the urve ln P versus 1/T .
lower and upper level of the mer ury olumn. The mi ros ope position an
Laboratory setup. The installation is shown be determined by ruler 17.
in Fig. 1. Container 1 lled with water serves The method of indire t measurement of L used in this experiment has
as a thermostat. The thermostat is heated by an important advantage over the dire t method. The dire t measurement
ele tri heater 2. The ooling is performed must be done at onstant pressure, so the ontainer annot be sealed. In so
by tap water running through helix 3. The doing it is impossible to ensure purity and reprodu ibility of experimental
air oming through tube 4 mixes thermostat onditions as in our experiment.
water. Water temperature is measured by However our installation has a signi ant drawba k: the thermometer
thermometer 5. The liquid under study is measures the thermostat temperature rather than that of the liquid under
Fig. 1. Installation for inside the sealed ontainer 6 pla ed in the study (or its vapor). These temperatures are lose enough only if heating
measuring heat of vaporization thermostat. Before the ontainer was sealed pro eeds slowly. One an verify that the rate of heating is not too fast by
it had been eva uated, so there is only the omparing the results obtained during heating and ooling the ontainer.
saturated vapor left above the liquid. The This omparison must be done. To be spe i , the rate of the thermostat
vapor pressure is determined by means of the mer ury manometer onne ted temperature hange should not ex eed 1 ◦ C for 13 minutes.
with the ontainer. The height of the mer ury olumn is measured with the
aid of a mi ros ope.
174 PHASE TRANSITIONS
LABORATORY ASSIGNMENT Chapter V

1. Measure the dieren e of mer ury levels in the U-shaped manometer with
the aid of the mi ros ope and the temperature with the thermometer.
2. Turn on the thermostat. In the installation 1 water in the thermostat is
SURFACE PHENOMENA
heated by the ele tri heater. Make sure that the air mixer operates properly.
Regardless of the installtion, you are working with, 1 or 2, measure the
pressure and the temperature ea h time the temperature in reases by one
kelvin.
Keep in reasing the temperature during one half of the available time,
so that you have enough time to do the measurements when ooling the
thermostat. The maximum water temperature should be 4050 ◦ C.
3. Repeat the same measurements when the thermostat is ooled down. Set
Mole ules of liquid are attra ted to ea h other by the ele tri for es
the water ow rate so that ooling pro eeded at the same pa e as heating.
whi h exist even between nonpolar mole ules due to indu ed polarization.
4. Plot the experimental points in the oordinates T , P and 1/T , ln P . The Mole ules at the surfa e layer whi h is in onta t with a gas are pulled to
points obtained during heating and ooling should be plotted using dierent the bulk of liquid mu h stronger than in the opposite dire tion be ause of a
olors. signi ant gradient of density or on entration of mole ules. Therefore the
Cal ulate L using Eq. (4) and two sets of measurements. Do the results mole ules at the surfa e gain an additional potential energy ompared to
agree? Estimate the error. Whi h plot allows one to al ulate L with better those in the bulk.
a ura y?
The work σ required to reate in a reversible isothermal pro ess a unit
Questions surfa e area of liquid is alled the surfa e tension.
1. A referen e manual gives the heat of vaporization measured at the pressure of The origin of the term "tension"is due to another
760 mm Hg. Does the tabulated value orrespond to your result? Whi h value is denition based on the asso iated for e whi h an be
greater? Estimate the dieren e between them. illustrated by the following experiment with a liquid
2. Argue how the value of heat of vaporization hanges when temperature in reases. lm.
Consider a soap lm bounded on the re tangular
Literature
frame by a movable rossbar (see Fig. 1). Surfa e L
tension tends to redu e the surfa e area of liquid of
ë. VII, 104, 105.
a given volume in order to minimize therepla
PSfrag potential
ements
2. Ñàâåëüåâ È.Â. Êóðñ îáùåé èçèêè. Ò. 1. Ìåõàíèêà. Ìîëåêóëÿðíàÿ èçèêà.
energy. That is why to keep the rossbar in equilibrium ∆x
Ì.: Íàóêà, 1982. 126.
the external for e equal to 2f should be applied (the
3. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò. II. Òåðìîäèíàìèêà è ìîëåêóëÿðíàÿ
èçèêà. Ì.: Íàóêà, 1979. 113, 114. fa tor of two is due to the double surfa e of the lm).
4. Ù¼ãîëåâ È.Ô. Ýëåìåíòû ñòàòèñòè÷åñêîé ìåõàíèêè, òåðìîäèíàìèêè è êèíåòè
Let us in rease the for e f by an innitesimal amount 2f
êè. Ì.: ßíóñ, 1996. ×. II. ë. 6, 4. and move the rossbar at the distan e ∆x. The work Fig. 5.1
done is
Ñ. 152159. A = 2f ∆x.
Ì.: èçä-âî ÌÔÒÈ, 1998. Ñ. 244254. On the other hand, a ording to the denition of the surfa e tension the
work is equal to
A = 2L∆xσ,
where L is the rossbar length and 2L∆x is the in rement of the lm surfa e.
176 SURFACE PHENOMENA Chapter V 177

By equating both expressions we obtain ∂Ψtot
σ= . (5.7)
∂F T
f
σ= . (5.1)
L We integrate the last expression using the assumption that without any lm
the free energy is zero: Ψtot = 0 if F = 0. Therefore
We on lude that surfa e tension is equal to the for e a ting on a unit length
of the boundary of the surfa e area of liquid. The for e is parallel to the Ψtot = σF. (5.8)
surfa e and perpendi ular to the boundary.
It is worth mentioning that the surfa e phenomena are observed in a Substituting the above expression into Eq. (5.6) we obtain
very thin layer of liquid of the order of 10−7 m. This is due to rapid de ay
of the inter-mole ular for es with distan e be ause of their dipole nature. dσ
Therefore the surfa e phenomena an be studied in experiments with thin S = −F .
dT
liquid layers in luding liquid lms.
Then using Eq. (5.8) we nd from Eq. (5.4) the total surfa e energy:
Thermodynami s of surfa e tension. A ording to the denition of
surfa e tension the work σ is required to in rease isothermally the surfa e
dσ

area of liquid by one unit. Therefore this quantity represents Helmholtz free Utot = σ − T F. (5.9)
dT
energy per surfa e area (see Eq. (5.8)). Let us dis uss it in detail.
We use the rst (1.2) and the se ond (1.7) laws of thermodynami s for In the isothermal pro ess the in rement of the total surfa e energy Utot is
the thermodynami al des ription of the phenomenon. A ording to the rst proportional to the in rement of the surfa e area and a ording to the rst
law, δQ = dU + δA. The work of external for es required to in rease the law of thermodynami s (Eq. (5.2)) the amount of heat supplied to the lm
surfa e area of liquid by dF equals σdF whereas the work of the surfa e in this pro ess is
layer of liquid (the lm) has the opposite sign, δA = −σdF . Therefore the dσ
rst law of thermodynami s applied to the lm reads Q = ∆Utot − σ∆F = −T ∆F.
dT
δQ = dUtot − σdF, (5.2) The transferred heat per unit area equals
where Utot is the total surfa e energy. dσ

q = −T . (5.10)
In a ordan e with the se ond law of thermodynami s one an dene dT
entropy for any system as a fun tion of state, so dS = δQ/T is exa t
dierential. Using this and the rst law of thermodynami s we write the Mole ules of a surfa e layer are pulled into the liquid bulk, so in order to
total surfa e energy as exa t dierential: move a mole ule from the bulk an external work must be done. Therefore an
adiabati in rement of the surfa e area leads to a de rease of the temperature
dUtot = T dS + σdF. (5.3) of the liquid and the isothermal pro ess requires a heat supply. That is why
q is positive and a ording to Eq. (5.10) the derivative dσ/dT is negative,
Let us introdu e into this expression a free energy Ψtot whi h is given by i.e. the surfa e tension de reases with the in rease of temperature.
Ψtot = Utot − T S. (5.4) Noti e that in ontrast to the surfa e tension the total surfa e energy
Utot of liquid weakly depends on temperature. Moreover, if there is some
We derive temperature range in whi h σ dependen e on T an be approximated by
dΨtot = −SdT + σdF. (5.5) a straight line σ = a − bT , one gets from Eq. (5.9) that Utot = aF , i.e. a
onstant value. However in a broader range of temperatures the dependen e
This is an equation in exa t dierentials, therefore
of σ on T is essential: in the vi inity of the riti al point any distin tion
∂Ψtot between the liquid and its vapour vanishes and the surfa e tension and the
S=− , (5.6) surfa e energy tend to zero.
∂T F
178 SURFACE PHENOMENA 2.5.1 179
ylindri al surfa e
σ
y ∆P = . (5.13)
C r
D
In general ase one should draw two mutually perpendi ular planes
L through the normal to the surfa e and nd the radii of the tangent ir les
PSfrag repla ements r1 and r2 . Then
1 1
∆P = σ + . (5.14)
r1 r2
α This equation is known as the Young-Lapla e equation.
A B The quantity (1/r1 + 1/r2 ) is the doubled mean urvature, it is
ϕ dα
ϕ 2 ϕ independent of the orientation of the perpendi ular planes drawn through
2 2
x the normal. In a parti ular ase of a spheri al surfa e of radius r we obtain
σL σL 2σ
r ∆P = . (5.15)
r
This formula an also be obtained by the approa h used to derive
Eqs. (5.11) (5.13).
Fig. 5.2. For es a ting on a ylindri al surfa e of liquid
2.5.1. Measurement of surfa e tension of liquid

Pressure under the urved liquid surfa e. A urvature of liquid surfa e
leads to the dieren e of pressures ∆P on the opposite sides of the surfa e Purpose of the lab: 1) to measure the surfa e tension of a sample
be ause of surfa e tension. liquid at dierent temperatures by using the known surfa e tension of
At rst, let us onsider a simple ase when the surfa e is a ylinder of the referen e liquid; 2) to determine the total surfa e energy required for
radius r and length L. Figure 2 shows the surfa e and its ross-se tion. isothermal reation of a unit surfa e area of liquid.
Consider the pat h ABCD of the surfa e whi h is symmetri to the axis y
Tools and instruments: Rehbinder devi e with a thermostat; sample
and subtends the angle ϕ. The sum of the tangential for es σL a ting at the
liquids; and glassware.
pat h sides is dire ted along y axis and is equal to
ϕ Surfa e tension results in a dieren e of pressure on two sides of a urved
fσy = 2σL sin . (5.11) interfa e between two media. An ex ess pressure inside a spheri al bubble
2
in a liquid is given by the YoungLapla e equation (Eq. (5.15)):
The pressure under the surfa e is greater by ∆P , so the for e a ting
on the small stripe of width rdα and length L at the angle α is dire ted 2σ
∆P = Pinside − Poutside = . (1)
along the radius and equals Lrdα∆P . Its omponent along y is equal to r
Lrdα∆P cos α, so the net for e along y axis is given by the integral
This is the main formula for the method of measurement of the surfa e
Z
ϕ/2 tension of liquid used in this experiment. One measures the pressure required
ϕ for reating a gas bubble in the liquid.
fpy = Lr∆P cos αdα = 2Lr∆P sin . (5.12)
−ϕ/2
2
Laboratory setup. The sample liquid (aniline) is poured into ontainer
B. Container E is lled with distilled water. Both ontainers are plugged. A
In equilibrium fσy = fpy and applying the obtained equalities we get for the hollow metal needle C passes through the plug of the ontainer E with its
tube leads to a noti eable drop of temperature of the surfa e layer ompared
C to the bulk of liquid. Se ondly, thermal expansion leads to a rise of the liquid
level when temperature grows. Thus reated hydrostati pressure lessens
the ee t of the YoungLapla e pressure de rement due to σ redu tion, for
example in experiments with aniline the sign of the investigated phenomenon
E hanges when the liquid olumn rea hes the height of about ve entimertes.
K2 B Both errors an be made negligible by pla ing the tip of the needle lose
A C to the ontainer bottom. In this ase, the net pressure measured by the
manometer equals P = ∆P + ρg h. Noti e that the value of ρg h is virtually
K1
independent of temperature sin e the rise of a liquid olumn is ompensated
D by the de rease of its density (the produ t ρh is determined by the mass of
liquid in the ontainer and is therefore onstant). The value of ρg h should
be determined experimentally by two methods. Using the rst method one
measures the value of P1 = ∆P ′ when the needle tip just tou hes the liquid
surfa e. Then one pla es the needle lose to the bottom and measures the
magnitude P2 = ρg h + ∆P ′′ at the same temperature. Be ause of the liquid
in ompressibility one sets ∆P ′ = ∆P ′′ thereby obtaining ρg h = P2 − P1 .
M
Using the se ond method one measures the depths of the needle immersion
h1 and h2 with a ruler during P1 and P2 measurements, respe tively. This
Fig. 1. Setup for measuring temperature dependen e of surfa e tension an easily be done by measuring the distan e between the upper end of the
needle and any point of the setup.
tip immersed into the liquid and the upper end opened to the atmosphere. If Remark. The manometer has a high sensitivity, so it is important to
the se ond ontainer is airtight, the underpressure in the ontainer E would operate it properly. All adjustments in the setup should be performed only
ause the air bubbles gurgling. Thus the surfa e tension an be determined after the manometer toggle swit h is set to atmosphere.
from the value of the underpressure required to reate the bubbles in the In parti ular, a similar operation should be done before lling the
ontainer E. aspirator A with water. Otherwise when the aspirator is being lled the gas
When the tap K1 is slightly opened, the aspirator A drips water pressure in the system in reases, al ohol is pressed out of the manometer
produ ing the underpressure whi h is measured with an in lined al ohol tube, and air bubbles are aptured in the onne ting pipes of the gauge.
manometer M. The readings of the manometer multiplied by the oe ient This violates the manometer alibration and leads to invalid readings.
dependent on its slope (usually 0.2) give the pressure in kp/m2 (1 kp/m2 = 9.8 Pa). LABORATORY ASSIGNMENT
Water reserve is replenished by turning the tap K2 thereby onne ting the 1. Make sure the setup is operating properly. For this purpose, ll the aspirator
lower part of the aspirator to the atmosphere and to the upper part lled with water and he k that the needle is not stained with aniline (if this is
with water. the ase wash it rst with a etone and then with distilled water), then pla e
In order to stabilize the temperature of the sample liquid, water from the needle in the ontainer lled with water so that its tip just tou hes the
the thermostat ows ontinuously through the ooling ja ket D of the surfa e. Set the rate of water dripping at approximately 1 drop in 5 se onds,
ontainer B. and he k that the bubbles are being reated. The manometer must show
a gradual rise of pressure to some peak value and a subsequent rapid drop
Usually the needle tip only tou hes the surfa e of liquid to eliminate related to emergen e of the bubble.
the inuen e of the hydrostati pressure of a olumn of liquid. However, 2. Set the rate of the water dripping so that the peak pressure value is
in measuring a temperature dependen e of the surfa e tension a number of independent of this rate. The bubbles should not emerge too often (less
ompli ations arise. Firstly, the signi ant thermal ondu tivity of the metal than 1 bubble per 5 se onds).
3. Measure the maximum pressure just before a bubble gurgles. Estimate the 7. Does the experiment a ura y allow one to noti e a nonlinearity of the σ(T )
random error from the s atter of the results. Using the tabulated value of dependen e?
the surfa e tension of water determine the needle diameter. Compare it with 8. Whi h errors dominate in the experiment: random or systemati ?
the value measured dire tly. 9. Whi h value should be substituted into the formula for the height of the liquid
4. Install the needle in the aniline ontainer. Measure the peak bubble pressure olumn in the apillary: σwater−air or σwater−glass ?
when the needle tip just tou hes the aniline surfa e. Measure h1 . Literature
5. Submerge the needle as deep as possible (a small gap between the tip and the 1. Êèêîèí À.Ê., Êèêîèí È.Ê. Ìîëåêóëÿðíàÿ èçèêà. Ì.: Ôèçìàòãèç, 1976.
bottom should be left so that a bubble does not tou h the glass). Measure ë. VII, 98103.
the peak bubble pressure. Using the dieren e of the pressures obtained in 2. Ñèâóõèí Ä.Â. Îáùèé êóðñ èçèêè. Ò.II. Òåðìîäèíàìèêà è ìîëåêóëÿðíàÿ è
this and the previous measurements determine the depth of immersion of çèêà. Ì.: Íàóêà, 1979. 106109.
the needle tip. Measure h2 . Compare the measured value of ∆h = h1 − h2
with the one al ulated from ∆P .
Note: σ has weak dependen e on T . Therefore one should ll the
aspirator with water at room temperature almost to the top (taking into
a ount the remark above!), adjust the rate of the level rise in the manometer
measuring hannel, and maintain the rate onstant during the experiment.
This allows one to de rease the systemati error.
6. Previous measurements were performed at room temperature. Now study
the dependen e σ(T ) by heating the aniline. Swit h on the thermostat
and wait until the pre-determined temperature stabilizes. The temperature
in rement should be 35 ◦ C, be ause the temperature must not ex eed 60 ◦ C
while the dependen e must in lude 68 experimental points. The ¾Pump¿
button should not be swit hed o!
7. Repeat the measurements by ooling the setup down to room temperature.
Thermostat is ooled by running water.
8. Estimate the errors of pressure and temperature measurements.
9. Plot the dependen e of σ on T and determine dσ/dT from the plot. Estimate
the a ura y of the result.
10. On the same diagram plot the temperature dependen e of the heat q required
to reate the unit area of the surfa e (see Eq. 5.10) and the surfa e energy
per unit area Utot /F (Eq. 5.9).
Questions
1. If several bubbles are produ ed per se ond the manometer readings are pra ti ally
onstant. Does it make sense to measure it?
2. Why should one measure just the peak pressure?
3. Why an a thermal expansion ee t be redu ed by submerging the needle?
4. Why should the bubbles not tou h the bottom?
5. Is it possible to determine σ by measuring maximum and minimum pressures
during the bubble gurgling if the needle immersion depth is unknown?
6. Using the obtained results estimate the riti al temperature of aniline.
CONTENTS 185
CONTENTS Stationary thermal ondu tivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

Temperature jump . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Transport phenomena in liquids and solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Vis osity of liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Heat equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .63
2.2.1. Experimental study of mole ular diusion of gases . . . . . . . . . . . . . . . 64
2.2.2. Measurement of thermal ondu tivity of air at various pressures . . 72
2.2.3. Measurement of thermal ondu tivity of gases at atmospheri
pressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .82
Chapter I. THERMODYNAMIC PROCESSES . . . . . . . . . . . . . . . . . . . . . . . . . 2 2.2.4. Measurement of thermal ondu tivity of solids . . . . . . . . . . . . . . . . . . . 86
The rst law of thermodynami s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2.2.5. Determination of vis osity of liquid by its outow through
Work done by gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 apillary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Heat apa ity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2.2.6. Determination of a tivation energy of liquid via temperature
The se ond law of thermodynami s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 dependen e of its vis osity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Heat apa ity of ideal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.2.7. Experimental study of gas diusion through porous medium. . . . .107
Adiabati pro ess . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Polytropi pro ess . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Chapter III. MOLECULAR PHENOMENA . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Speed of sound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Flow of rareed gas through pipe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Van der Waals equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
The Joule-Thomson ee t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
Heat apa ity of solids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Osmoti pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
2.1.1. Measurement of spe i heat of air at onstant pressure . . . . . . . . . . 17
2.3.1. Creation and measurement of va uum . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2.1.2. Measurement of Cp /Cv ratio of gas by the method of adiabati 2.3.2. Experimental study of ion pump . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
expansion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.3.3. Measurement of osmoti pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
2.1.3. Determination of Cp /Cv ratio of gas by measuring the speed of
sound in it. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 2.3.4. S attering the slow ele trons on mer ury atoms . . . . . . . . . . . . . . . . . 148
2.3.5. Measurement of saturated vapor pressure of a refra tory metal . . 158
2.1.4. Measurement of spe i heat of solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.1.5. Experimental study of thermal ee ts aused by elasti Chapter IV. PHASE TRANSITIONS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .167
deformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.4.1. Measurement of vaporization heat of liquid . . . . . . . . . . . . . . . . . . . . . . 170
2.1.6. The JouleThomson ee t. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Chapter V. SURFACE PHENOMENA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
Chapter II. TRANSPORT PHENOMENA. . . . . . . . . . . . . . . . . . . . . . . . . . . . .53
Thermodynami s of surfa e tension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Transport phenomena in gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 Pressure under the urved liquid surfa e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
Average velo ity of mole ular motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 2.5.1. Measurement of surfa e tension of liquid . . . . . . . . . . . . . . . . . . . . . . . . 179
Mean free path . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .54
The number of ollisions with wall . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Diusion, vis osity, and thermal ondu tivity of gases . . . . . . . . . . . . . . . . . . . . . . . . 55

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Lab Practicum Part 2

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Chapter I 3

Work done by gas. Consider expansion of a gas

into the rst law of thermodynami s: Assume that U = U (T, V ). Then

The main properties of van der Waals equation an be onveniently

Laboratory setup. The setup onsists of the

dieren e resulted from the JouleThomson ee t with the temperature

Transport phenomena in gases

are onne ted by the simple relation

j = −D grad C, q = −κ grad T, (2.10)

2.2.1. Experimental study of mole ular diusion

Tools and instruments: an experimental installation; a low va uum

Diusion is a haoti propagation of mole ules be ause of their thermal

bridge. temperature jump an be ignored and Tr an be equated to the lament

Tools and instruments: an installation for measurement of heat

PSfrag repla ements 2

Before measurements one should turn on the thermostat (move the

LABORATORY ASSIGNMENT 2.2.7. Experimental study of gas diusion

Integrating this equation over time we obtain

ultimate pump pressure is ∼10−1 torr.

Air and many other gases an be treated as ontinuous media under

2.3.1. Creation and measurement of va uum

τ We an express ε as a fun tion of urrent I and its derivative I˙. To

S = 20 m2 we an determine the equilibrium surfa e density of mole ules

Laboratory setup. A devi e for measuring osmoti pressure is alled

dN/N , is equal to the ratio of this area to S :

σsol.sp. = π(r1 + r2 )2 . (3)

= σne−σnx dx = ρ(x) dx. À

A ording to the rst two laws of thermodynami s the dierentials of

Using Eq. (4.1) we nd: Equation (4.8) is alled Clausius-

Purpose of the lab: 1) to measure the pressure of saturated vapor of Ê m3

In what follows the volume V2 is denoted by V . The volume V enters

pressure is determined by a manometer, and

LABORATORY ASSIGNMENT Chapter V

where Utot is the total surfa e energy. dσ

Fig. 5.2. For es a ting on a ylindri al surfa e of liquid

2.5.1. Measurement of surfa e tension of liquid

CONTENTS Stationary thermal ondu tivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

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into the rst law of thermodynami s: Assume that U = U (T, V ). Then

dieren e resulted from the JouleThomson ee t with the temperature

2.2.1. Experimental study of mole ular diusion

Diusion is a haoti propagation of mole ules be ause of their thermal

bridge. temperature jump an be ignored and Tr an be equated to the lament

LABORATORY ASSIGNMENT 2.2.7. Experimental study of gas diusion

A ording to the rst two laws of thermodynami s the dierentials of

Using Eq. (4.1) we nd: Equation (4.8) is alled Clausius-