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H Quizzagan1
1
Bachelor of Science in Physics
Department of Physical Sciences
University of the Philippines Baguio
Email: quizzaganharlee10@gmail.com
1. A container of volume V contains N molecules of a gas. We assume that the gas is dilute so that the
position of any one molecule is independent of all other molecules. Although the density is uniform
on average, there are fluctuations in the density. Divide the volume into two parts V1 and V2 with
V = V1 + V2 .
Let us illustrate the said problem as follows:
Figure 1: Gas molecules in volume V .
We can try to treat this as a Random Walk Problem such that a molecule is either on V1 or in V2 but
the former location does not affect that later one. For this to work, we have to check the following
definition of variables:
p = probability that a molecule is in V1
(1)
q = probability that a molecule is in V2
(2)
(3)
(4)
(5)
(6)
Hence, if we use the definitions described in (1) to (5), then we know that
N = N1 + N2
(7)
Hence, by simple statistics, the probability p that a molecule can be found in V1 is simply the
number of chances by which a molecule is in V1 divided by the total number of possibilities that
it can be found anywhere in the volume V . We can represent this as:
p=
V1
V1
=
V1 + V2
V
(8)
(b) (2 points) What is the probability that N1 molecules are in V1 and N2 molecules are in V2 , where
N = N1 + N2 ?
SOLUTION:
Let us declare that WN (N1 ) denotes the probability that there is an N1 number of molecules that
can be found in V1 an that WN (N2 ) is the probability of finding N2 number of molecules in V2 .
Note that we can treat this with a Binomial Distribution which we know to be denoted as
WN (N1 ) =
N!
pN1 q N2
N1 ! N2 !
(9)
Furthermore, we should note that for the definition we stated on (1) and (2), we have the following
condition:
p+q =1
(10)
but there is no assurance that p = q. Hence, we cant utilize this assumption.
Hence, for this case, we have the following:
WN (N1 ) =
N!
pN1 q (N N1 )
N1 ! (N N1 )!
(11)
N!
q N2 p(N N2 )
N2 ! (N N2 )!
(12)
N!
WN (N2 ) =
N2 ! (N N2 )!
V1
V
N1
V1
1
V
V1
1
V
N2
V1
V
(N N1 )
(13)
(N N2 )
(14)
(15)
but we know that the denominator, which is the sum of all probabilities for all possibilities
(molecule is in either V1 or V2 ) is simply 1. Hence, we have,
f (u) =
M
X
f (ui )P (ui )
(16)
N1 W (N1 )
(17)
i=1
N
X
i=0
N
X
N!
N1 =
N1
N
!
(N
N1 )!
1
i=0
V1
V
N1
(N N1 )
V1
1
V
(18)
We know from Chapter One in Reifs textbook that this leads to a simplified expression of the
form:
N1 = pN (p + q)N 1
(19)
but we know from (10) that this simplifies further to
N1 = pN
(20)
which describes the average number of molecules that can be found in V1 . Similarly,
N2 = qN
(21)
V1
V
N1 =
N2 =
N
(22)
V1
1
N
V
(23)
(d) (3 points) What are the relative fluctuations of the number of molecules in each part?
SOLUTION:
In order to compute for the relative fluctuations of the number of molecules in each part, we simply
2
calculate for the dispersion (N1 )2 and divide it with N1 . Again, from Chapter One, we know
that
(x)2 = (x x)2 = x2 x2
(24)
We reconfigure this for us to use
(N1 )2 = N12 N1
(25)
(26)
Now, we simply rewrite (26) using (8) and (10). Hence, we have
V1
V1
(N1 )2 = N
1
V
V
(27)
N
=
V1
V
V1
1
V
N1
(28)
V1
N1 1
V
N1
1
=
V1
V
N1
(29)
Similarly,
(N2 )2
N2
V1
1
V
N2
(30)
(32)
V1
0. Hence, we have:
V
(N1 N1 )2 N (0)(1 0)
(33)
(N1 N1 )2 0
(34)
2. Consider an isolated system consisting of a large number N of every weakly interacting localized particles
1
of spin . Each particle has a magnetic moment which can point either parallel or antiparallel to an
2
applied field H. The energy E of the system is then E = (n1 n2 )H, where n1 is the number of
spins aligned parallel to H and n2 is the number of spins aligned antiparallel to H.
SOLUTION:
Before we start solving the problem, let me note that I adopted the recipe described in Chapter Two of
Reif in analyzing systems similar to this. Firstly, we have to describe the state of the entire system. Note
that for each particle in the system, the quantum number m which tells us about the spin orientation
of each particle can only assume the values
m=
1
2
(35)
as for each particle, it has only two possible spin orientation which is either up or down. Hence, the
state of the system is the quantum number m fir each of the N particles which we can denote as
m1 , m2 , m3 , ..., mN
(36)
(37)
(38)
N = n1 + n2
(39)
Let
(a) (5 points) Consider the energy range between E and E + E where E is very small compared to
E but is microscopically large so that E H. What is the total number of states (E) lying
in this energy range?
SOLUTION:
We can treat this with the binomial distribution as we have two sets of possible values for our
parameter, the quantum number m. Hence, we have the following number of distinct possibilities
where you have n1 number of spins paralle and n2 number of spins anti-parallel to H:
(E) =
N!
(n1 )!(n2 )!
(40)
Recall from Chapter Two in Reif that the total number of states (E) in the range between E
and E + E is expressed as
(E) = (E + E) (E) =
E
E
(41)
wherein (E) is the total number of possible sets of values of the m quantum numbers which we
denoted in (40). Therefore,
E
N!
(42)
(E) =
(n1 )!(n2 )! 2H
We note that
E = (n1 n2 )H
(43)
(44)
N H E
N
E
=
2H
2
2H
(45)
(46)
N
E
E + N H
=
+
2H
2
2H
(47)
+
!
!
2
2H
2
2H
(48)
(b) (5 points) Write down an expression for ln (E) as a function of E. Simplify this expression by
applying Stirlings formula in its simplest form.
SOLUTION:
We simply get the natural logarith of (48) and apply rules on natural logarithm. We have
ln (E) = ln
N!
E
+ ln
(n1 )!(N n1 )!
2H
ln (E) = ln N ! ln n1 ! ln (N n1 )! + ln
(49)
E
2H
(50)
Recall that Stirlings formula gives us a way to approximate such a form of expression with
ln n! = n ln n n
(51)
E
2H
(52)
This gives us
ln (E) = N ln N n1 ln n1 (N n1 ) ln (N n1 ) + ln
E
2H
(53)
We can expand the third logarithmic term using Taylors series such that:
y
ln x + y = ln x + ln 1 +
x
(54)
Now, we have
h
E
n1 i
+ ln
ln (E) = N ln N n1 ln n1 (N n1 ) ln N + ln 1
N
2H
(55)
(58)
n1
E
n1
+ (n1 N ) ln 1
+ ln
N
N
2H
(59)
E
N
H
(60)
Hence, we can use this to rewrite the terms in (59), such that,
1
E
1 N
E
N
E
1
E
E
ln (E) =
N
ln
N ln
1
+ln
2
H
2 N
N H
2
2H
2
N H
2H
(61)
This simplifies to
1
E
1
E
1
E
1
E
E
ln (E) =
N
ln
1
N+
ln
1
+ ln
2
H
2
N H
2
2H
2
N H
2H
(62)
(c) (5 points) Assume that the energy E is in the region where (E) is appreciable, i.e., that it is
not close to the exteme possible value N H which it can assume. In this case, apply a Gaussian
approximation to part (a) to obtain a simple expression for (E) as a function of E.
SOLUTION:
For this system, we note that N . For such a case, we know the the Gaussian distribution
provides an approximate expression of the probability since this distribution has a pronounced
maximum at a certain value. If we consider a region that is near this maximum point (near but
not too close), then we can approximate the probability function as a continuous function of the
continuous variable n1 with only the integral values having physical relevance.
We recall from (4) that
f (n1 ) =
N!
(n1 )!(N n1 )!
(63)
In this case, we expand the ln f (n1 ) because its slowly varying compared to just f (n1 ) and hence,
we see that the power series of the natural logarithmic function converges more rapidly than for
6
the f (n1 ) which is what we want. Hence, we expand this around the maximum which we denote
as n
= n( max). We use Taylor series expansion to get
1
ln f (n1 ) = ln f (n1 ) + B1 + B2 2 + ...
2
(64)
dk ln f (n1 )
Bk =
dnk1
n1 =
n
(65)
such that
d
f (n1 ) = 0 at this maximum
dn1
point. We can also ignore the higher order derivatives in (64). Hence, we end up with
Hence, we know then that the second term in (64) vanishes because
1
ln f (n1 ) = ln f (n1 ) + B2 2 , = n1 n
(66)
As we can see, we can just get the exponential value for each side to end up with a value of f (n1 ).
e
ln f (n1 )
=e
ln f (n1 )+
1
B2 2
2
1
|B2 | 2
f (n1 ) = f (n1 )e 2
(67)
(68)
You might be wondering why in (68) there is a negative exponent. As we can see from (65), B2
denotes the second derivative of f (n1 ) with respect to n1 evaluated at the maximum n1 . From
Math 53, we know the the second derivative of a function tells us about the curvature at that
point and in this case, the curvature at the maximum should be less than 0, hence
B2 = |B2 |
(69)
Note that f (n1 ) is integrated over all values of n1 and this should give us the sum total of all
possibilities of spin direction. Therefore, we know that
Z
1
|B2 | 2
d = 2N
f (n1 )e 2
(70)
How do we determine the contant f (n1 )? Note that f (n1 ) and n1 could be treated as though
they are quasicontinuous variables. Hence, the treatment we did above.
Z
f (n1 )
1
|B2 | 2
2
d = 2N
e
(71)
(72)
Hence,
s
2
= 2N
|B2 |
r
|B2 |
n
f (n1 ) = 2
2
f (n1 )
(73)
(74)
We recall again from Math 53 that the first derivative of a function tells us about the slope of the
tangent line at that point. In our case, the first derivative evaluated at the maximum should be
equal to zero. We use the first and second term only of (59) to evaluate this.
B1 =
d ln f (n1 )
d h
n1
n1 i
=
n1 ln
+ (n1 N ) ln 1
dn1
dn1
N
N
(n1 )
dn1
N
dn1
N
N dn1
(75)
(76)
1
n1
, du =
N
N
(77)
(78)
dn1
N
du
u
n1 N
(79)
d h
n1 i
N 1
n1
n1
n1 ln
= n1
ln
= 1 ln
dn1
N
n1 N
N
N
(80)
Hence,
second term:
d
n1 d
d
n1
n1
= (n1 N )
+ ln 1
(n1 N ) ln 1
ln 1
(n1 N )
dn1
N
dn1
N
N dn1
where we again used the multiplication rule of differentiation.
let
n1 du
1
u=1
,
=
N dn1
N
Hence, the first term in (80) can be rewritten and we have
N
n1
d
n1
1
= (n1 N )
+ ln 1
(1)
(n1 N ) ln 1
dn1
N
N n1
N
N
d
n1
n1
(n1 N ) ln 1
= 1 + ln 1
dn1
N
N
(81)
(82)
(83)
(84)
n1
N n1
+ 1 + ln
N
N
(85)
(86)
(87)
Hence,
n1 = N n1 n1 =
8
1
N
2
(88)
We use the expression obtained in (85) to get the second derivative which is simply
dB1
1
1
B2 =
=
dn1
n1
N n1 n1 =n1 = N
2
B2 =
2
2
4
=
N
N
N
(89)
(90)
Now we combine our results from (74) and (90) to finally rewrite (68):
1
|B2 | |B2 |2
2
e
2
(91)
1 4
(n1 n1 )2
4 1
e 2N
N 2
(92)
r
f (n1 ) = 2
r
f (n1 ) = 2
r
f (n1 ) = 2N
Recall that (E) = f (n1 )
2
e
N
N
2
n1
N
2
(93)
E
N
E
, then using n1 =
r
(E) = 2N
2
E
2
E
N 2H
e
N
2H
(94)
3. Consider two spin systems A and A0 placed in an external field H. System A consists of N weakly
1
interacting localized particles of spin and a magnetic moment . Similarly, system A0 consists of N 0
2
1
and a magnetic moment of . The two systems are
weakly interacting localized particles of spin
2
then placed in thermal contact with each other. Suppose that |b| 1 and |b0 | 1 so that
ln (E) =
E2
22 H 2 N
ln 2
+Nr
N
(95)
=
ln [(E)]
(96)
E
Using (95), we have:
1
E
= 2 2
(2E) + 0 = 2 2
(97)
2 H N
H N
and we know that
=
1
kT
(98)
Hence,
1
E
2 H 2 N
= 2 2 E=
kT
H N
kT
We also know that
E0 =
9
02 H 2 N 0
kT 0
(99)
(100)
(b) (3 points) In the most probable situation corresponding to the final thermal equilibrium, how is
of system A related to the energy E0 of system A0 ?
the energy E
SOLUTION:
In equilibrium, we know that:
= 0 T = T 0
(101)
Using our results from (99) and (100), we see that
2 H 2 N
E
kT
=
E0
02 H 2 N 0
kT
(102)
2 N
E
= 02 0
0
E
N
(103)
Simplified
(c) (3 points) What is the heat Q absorbed by system A in going from the initial situation to the
final situation when it is in equilibrium with A0 ?
SOLUTION:
We know the energy is conserved which can lead us to the safe conclusion that
E + E 0 = N H + 0 N 0 H
(104)
E = N H + N 0 H E 0
(105)
E02 N 0
2 N
(106)
(107)
(N H + 0 N 0 H)(2 N )
(2 N + 02 N 0 )
(108)
(109)
(110)
(N H + 0 N 0 H)(2 N )
N H
(2 N + 02 N 0 )
(111)
(N H + 0 N 0 H)(2 N ) N H(2 N + 02 N 0 )
(2 N + 02 N 0 )
(112)
N H2 N + 0 N 0 H2 N N H2 N N H02 N 0 )
(2 N + 02 N 0 )
(113)
Q=
We expand simplify (111)
Q=
Q=
As we can see, the first and third term of the numerator (113) cancels out and we are left with
Q=
N 0 H2 N N H02 N 0 )
(2 N + 02 N 0 )
(114)
(N 0 N H)(0 2 02 )
(2 N + 02 N 0 )
10
(115)
(d) (3 points) What is the probability P (E)dE that A has its energy in the range between E and
E + dE?
SOLUTION:
Recall that
P (E) (E)0 (E0 E), E0 = N H + 0 N 0 H
(116)
The total energy E0 is as we calculated (104) as E + E 0 .
Now, if we get the exponential value of both sides of (95), then we get back to the function (E).
Let use the first term of that as our proportionality variable such that
P (E) e
E2
22 H 2 N
(E0 E)2
22 H 2 N
(117)
E2
(E0 E)2
22 H 2 N 22 H 2 N
P (E)dE = Ce
(118)
We then normalize using the condition to determine this constant such that
Ce
(E0 E)2
E2
2
2
2 H N 22 H 2 N
11
dE = 1
(119)