L ~ l , \'

l\la.,. well Distribution of J\,folcculnr Velocifies les the molecular veJocities ·k

~ .1s,· , O f gaseous mo Iecu ' eep on
As a result of random l.:oll ions • , velocity component u. Then, the kinet · Chctng·
. I Of mass m havmg ,1 . • .h th' ic en in1,
Consider a gas molecu e • . 1 11 2 The probab1hty t at 1s molecule h . erg~ c.
. .. . . ~ mponent is Tm . . as It ,'
associated w1th tlus vel<..)Ctty l:O . . b p(tt) In the 19th centur; Boltzmann had s·h s ve1 00.-,
component between 11 an 11
d +du 1s given Y was
6
· ,proport10naJ toy__~ €, T
. I t 1s
• apparent tnown. tha "tr
probability for a molecule ro hav~ _~nergy at .
. - r.!kT e - mtil2kT ( ··
00
p(u) oc e · £ ::::: 112
fllul)
-mu 2 /2kTd
or p(_u )du = Ae u . . ...(2i
where A_ is the constant of proportionality. This constant can be evaluated by requ1nng that the lo~:
probatnbty must be urnty . Thus,
= Af +coe- rnu212kTdu= 1
f +oop(u)du
-00 -00

The range of integration of velocity component u is -cot? + co since vel_o~ity has both magnitude a
•·,(23)

direction. The integral in Eq . 23 can be easily evaluated. Settmg m/2kT=a, it 1s found from calculus tb;d
12
kT)'
f~+co
~
2
e-au du = ( 1t Ia)112 =
( 2 ;n

112
•- .(24)
From Eqs. 23 and 24, A(2rrkT/m) 112 = 1 so that A = (m/2nk]) ... (2))

Substituting for A in Eq. 22 , we have

1/2
P
(u)du =( m ) e - mu2/2kTdu
... (26)
2nkT
. Eq . 26 is called th~ ~ax~ell distribution of mo_lt~cu1~r velocit~es in .one dimension. It is easy 10
denve the Maxwell 's d1stnbut10n of molecular veloc1t1es m three dunens1ons by multiplying the three
one-dimension distributions with one another. Thus,
p(u,v,w) = p(u) p(v) p(w) ... (27)
where v and ware the velocity components in the other two dimensions .
p(u,v,w)du dv dw = p(u)duxp(v)dvxp(w)dw
_( m ) 312 [ m(u 2 + v 2 + w 2) ]
- 2nkT 2kT exp - du dv dw ...(28)
We are, however interested in an · h. •. •
between c and c+d (c2- 2 2 2 expression w ich gives the fraction of molecules with a veloctfy
points he within a iphe -:-- u
1 1
+; 7
w ) r~gaTdless of the ~irection . These are molecules whose velociey
which is the integral of ~~~vJwe in~ th1 ckness de at a distance c . This shell has the volume 41tc2dc,
q. 28 over the spherica] shell. Hence , we find that
312
p(c)dc == 4 ( m ) _?
. 7t 2nkT c exp (- mc2!2k1)dc ...(29)
This result was obtained by M .
velocities. It is customary to writ:xw;IJdm 1860 and is called the Maxwell distribution of molecular
The quantity dN!N (or p(c)dc) gives~ cf c a~ dN!N, where N is the total number of gas molecules.
e raction of molecules with velocity between c and c+dc. The
 EGA-'tLI'-- - ,,., . . 400 m:~i ,.
~ MINA where MIS the molar mass and
s ,n == . , . ·
1ecular rnas 0 be written as NA is the Avogadro s number. Accordingly,
f11
0
29 rnaY as 1
Bq- dN ( M ]3 12
p(c)dc = - . -
N
=. 4n
2rrRT
,? exp ( Mc
- - de
2
J .. .(30)
2RT
rviaxwell distribution of molecular
fbe . plotted in Fig. 1.
Jocities ,s
ve (hat the fraction of molecules Cl) Most probable velocity
We see ·than . ~

loc ities greater zero mer.eases .J

irJCI ve • ::i
tJaV increase in ve 1oc1ty, reaches a
i, u
Ul
with_an and then falls off towards zero .J
0
ma~unu~igher velocities .
again at
The important feature s of the curves ~f
u.
0
s follows :
z ·
are a ...o
!-
I. The fraction o~ ~nol ~c ulc s with too u
high veloc1t1es 1s very small. <
a:
loW or 100 · U,

z. 11iere is a certain ~elocit~ fnt which

uic fraclion of molecules 1s max imum Tiiis
is culled the most probahl e ve loc Jty
The most probnblr \ elocit y of a ga,
1 VE LOCITY --►

is the veloc ity possessed hy max 1mum Fig. I. 1ne Ma:., well' s distribution of molecular vclocltlcN .
nulllber of molecules l1f the gas al a given
iemperature. It corresponds tt, the r-cak nf the cu rve fl~ value. at a given temperature , depends upon
the volu111e of d1e gas.

Effect of Temperature on l>ist ri hut ion of ,1otccular Velocities. The most probable velocity
increases with ri se in temperatu re . as sho,l,n in Fig. I. The entu-e distribution curve , in fact , shifts
to the right wilh ri se in tempera ture. a~ ~hown . The rise in temperature , therefore , increases the
fraction of the molecules hav in e_ high vd oc11 ics considerabl y. This can readily be understood from the
prt'sence of the factor. expt- m2-rJ.J.:T) . 111 Eq. 29. The exponent has a negative sign and the temperature
Tis in the denominator. The fa ctor. therefore. increases markedly with increases in temperature .
Tbis factor is known as tJ1e Boltzmann factor .

tlrefur~r
Further. knowing that
~
+- mc2 is the kinetic energy of one molecule of the gas having velocity c,
exp (-mc?IJ.17) = exp ( - E:lk7) ...(31)

+
where c ( = mc2 ) 2:ives che kineric energy per molecule of the gas . The greater the temperature,
the greater is the val~e of £ . Hence. there is rapid increase of the Boltzmann factor with increase in
temperature . This conclusion finds application in the theory of reaction rates also.

Maxwell Distribution of ~lolendar Kinetic Energies . With the help of Eq . 29 i~ is poss ible to
know how the kinetic energies of rranslarion of molecules are distributed amongst the _various molecules .
The fraction of molecul es... hav ino kinetic enereies in the range of £ aoci £+d£. viz.. dNr! N, can be
det · :;) ..
ennmed as fo llows :

c = + mc2 or c:2- = (2d m)

...(32)
2cclc = (2/m)(dt ) or cclc = dd m

- mc) (d
(2 -mtl _
112
lbUs ffi312 de ...(33)
c-dc -- c -rh-
.,
I

m -- . - (m)
Suh,tnutm.g \he a\\\)\\' vahu: l \f tJ d< in Eq. l lJ . we have
t!N, ( 111 JJ/2 (. ~ Jde exp (- _£_)
p(,--) ck =N = 4 rr 2 rrk T 111 312 kT

= 2 ✓!; 12
exp ( - krT;: ) de
/;r (kT) J
Th1s is the Maxwrll distribution of molecular kinetic energieS.
E.xa:mplc 2. Calculate the fraction of oxygen molecules at 1 atm and 270c whose kinetic ener
~ of (s - 0·005b1 and (£ + 0·005£). . . . gJes l4: i~r
Solution : According to the Maxwell 's distribution of molecular IanetJc energies, .,

dN€ -
N -
2.fi
/;(kT) 312
exp (-_!_J
kT
d&

At. 27°c , kinetic energy of the gas is given by

21
E = 3/2 (l ·38 x 10-23 J K- 1) (300 K) = 6·21 X 10- J
· _73
dE = (£ + 0·005&) - (c - 0·005c) = 0·0lc = 6-21 x 10 - J
Substituting these va1ues in Maxwell's equation (35), we have

2(6 ·2lxl0- J)
,:____----=------=-~
21
} x
112
{ exp (
10- J
6-21 X
21
6 ·21 10-J J
J
dNc _ _ _ _
N { 23 1
- 1-77[(1 -38 X 10- JK- )(300K)]
312 1-38x10- JK- 1 x 300K <
23 x - J))
2 X 0 -788 10-lO r 1
X
= 1·77 x 0 -266 x 10-30 exp (-1·5)x6 ·2lxl0-23 J

= 4·647 X 10-3
The Max welJ distribution of kinetic energies at two
different temperatures is shown in Fig . 2 in which the
factor ( l/N) (dNJd£) is plotted against &. As can be
seen , the most probable kinetic energy increases with
increase in temperature as expected . The maximum in
tJ1e probability function corresponds to the most probable
kin.e1ic energy.
. It can be easily shown with the help of Eq . 35 that
(I) the most probable kinetic energy is given by kT/2
P_~r molecule or . R~/2 per mole of the gas and
(u) the average kmet1c e~ergy per mole is given by KINETIC ENERGY , c ~
(:/2 )NAkT= ~3/2)RT. Th1s result js, evidently' in Fig. 2. Maxwe.ll's qistribtJJjon of ldnetic ener~esat
aereement with that obtained from the kinetic th two, diffei:ent temperatures.
(Eq. 21) . . eory