Hislopia Journal 3 l2l?

OLO L57-L6+

VAN DER WAALS EQUATION: AN INTERACTTVE APPROACH

S W ANWANE
Department of Physics, shri shivaji Education society Amravati,s science
College, Congress Nagar, Nagpur 44OOL2

Abstract Almost all text books deal with the Van der waals equation and is riddling
in literature since 187o. This equation is widily appreciated. For
beginners the difficulties in assimilation are appreciated and addressed
for in-depth understanding. Graphical visualization along with analytical
approach is used in a collective way.
Koywonos Real gas equation, cubics, equation ofstate, analytical solution, iteration
etc.

Introduction
rft- -;::---:;
'qr
- x..................... (2)
The subject Kinetic Theory I t:
-t:
)

of Gases is popular in Or if the pressure and volume were

undergraduate Physics curriculum.
Van der Waal's equation of state is
well familiar. The present work
attempts an approach to enhance
assimilation.
Van der Waals'equation of
state for real gas
Van der Waals'equation is
{ volume is required to be found. A
t.P -;J-\ {L: - b) : rtl ..........,(1)
where P is the pressure, V is the
volume, T is the absolute
temperature, Ris the gas constant,
and a and b are constants that
depend upon the gas.
In the usual situation aand
b are known and can be found in
tables. One must watch the units
used thoggh. Usually c is in liter2
atm mole -. Similarly b is most often
in liter mole'. Thus it is usually
convenient to work in liter-atm anrl
to take R=0. 0820578 liter-atm/
mole-kelvin.
In a problem, if the volume and
temperature were known and the
pressure were needed, we simply
use (1) in form
known and the temperature were
needed:
n-!{n L i Jt
J
- -i91 J- -,{J lt' - sJ ...........(3)
The issue turns really
troublesome when pressure and
temperature are known and the
look at equation (1) shows that V
occurs in two different places. It is
not linearin 7. A closer look reveals
it to be cubic in V.
Solving cubics is not as
simple as solving quadratics. There
is a "cubic formula", but it is quite
messy and takes a large amount of
work. (See Appendix A for readily
understanding cubic messy
behavior,)
Van der Waals'equation for
the volume is a cubic and cubics
may have three roots. If exists, one
is guaranteed to be real and hence
meaningful; the other two can be
either real or complex. We are not
concerned with the imaginary root
as it is of less physical meaning as
leads to complex volume.
S W ANWANtr 158

Solving van der Waals' get a meaningful insight and

Equation for the Volume " The assimilate the Van der waals
General Problem equation.
We can re-write equation (1) Let us consider following
substitutions to re-form Van der
(e *;J g' -b) - nr: # ....(4) waals equation;

Now finding avalue of Vthat F :::. ...............(6)

fits with given values of Pand lfor l:

a given gas is the problem of finding r_ -'t'

a V th.at makes the left-hand side ftT
of equation (4) equal zero.ln a more n-l
-! l"
standard mathematical notation we -
ls
-

can call the right-hand side of t_4

equation (4) f (V). Then what we :1rr
want is to find a Vsuch that -IJ

This will simplify the form

f(1") = o ........................... (s)
This sort of problem is well-
known in mathematics. It is the
problem of finding a roof of equation
(5). In the general case /(I/) could
be any function. In some few of
these cases (linear equations,
quadratic equations) an analytic
solution can be obtained easily. In
others (cubics, quartics), analytic
solutions are known, but they are
often too messy to use. And in most
cases, there is no analgtic solution
at all. Appendix A presents three
roots. In turn it depicted to show
how messy it is!
Here a mathematical
modeling tool Maple 14 is used to
deal with the problem to support
our analytical approach that can
of equation;
t
.?I
Above equation (7) can be
solved in form (5) to obtain three
roots. The family of equations and
corresponding curves depends
upon parameters f and w. These in
turn play a vital role in deciding
roots like; real OR complex. These
two parameters depend upon
temperature and constants for gas
species respectively. Here follows
Table 1 that depicts arbitrary
choices that yield interesting
results. Effect of parameter f and
ru on roots and trend of reduced
variables x and y are presented in
Fig. 1.
VAN DER WAALS EQUATIoN: AN INTERACTIVE APPROACH
159

Table 1

1.0000 1.0000 2 Complex GnJl)/2

0.5000 0.5000 2 Complex 0.sri 0.866
0.1250 0.1250. 2 Complex 0.sti 0.866
0.0100 0.0005 2 Complex 0.0251i O.2222
0.0005 0.0005 2 Complex 0.5+i 0.866
1.0000 5.0000 2 Real @Jr)/2
1.0000 7.5000 2 Real 6.31 1,1. lgg
1.0000 10.0000 2 Real 51JI5

P1"*1 erl4I
t1
\]
"1
u"ll i,

il 1

i t1
I
L .t
I
1
,,1* *1.;:.;i*-l-i
l l:);ft
1,
,l
1

"t 1

j Ii,
"l ,1
|1
,,,

I
'..
)i,:
ri
i't.. ' a.1i
ii
tL*-*-*-** ---.. ..
.r1.1
1:

:;L;;**f
jj*1
-!

el,*a
,1
ll
'1r
1.
+t:* -:' .
..?'"
, i r : $
,
I
1

i
1:
,i
i
t:
i
'.1 .1:

i
i:
i
j
rL
 160
S W ANWANE

tl.3
,' ,.| i
" 1,1:

i:'.
.i
'-i
i:"
1: : ..1. 4 7 4
.t,. :
''
.1 1a
ti:
"il
'1:
it
1):

,i),
t.
i

parameters
Fig 1. Ptot of eS (7) for a variety of t and ur

Case 1
Let us ana|yzelast equation (7) and its 1"., 2,0 order differentiation
(visual) way for arbitrary constants' say
f : i*': : l'
in a graphical
ji;;il;.;r: iil

rlcntrantcr
:-T-,=

derivatives 1st and 2nd

Fig.2 A Piot of Function y=f(x)=1/(x-1)-1 lxn2 ' its
order
This form has two comPlex and minima analYticallY found and
jt'=E graphicallY visualized.
roots :.{ : t
and is asymptotic The literature has dealt with
T
to x-axis. This solution has no approach of iteration methods
physical significance in reference to liimerical aPPro ximationl like
and is caPable of
iinait g volume of the gas that we Newton's [1,2]
reailylntend to do. Its 1"' and 2"" practically estimating V. Arbitrary
order derivatives are also present starting proposed is required to be
in the Fig.2. APPendix 2 deals with ptopo""d in Newton-RaPson's
a cubic function that has a maxima method. Here, one can use ideal gas
 VAN DER WAALS EQUATION: AN INTERACTIVE APPROACH 161

expression to obtain first guess equation (7) that probably readers

, instead of random choice. More might have.overlooked in Fig.1. At
closer point to the root can be found inflation, 1"'and 2"0 order derivative
using equation (8). of equation (7) should vanish out.
Let us search such point
v
t., -f (v)
t./t+t - Y,- analytically and then try locating
/(D ....(8) it.
A couple of such steps help tw
one reaching root or at-least fairly
closer to the root that can solve a
'y:--- x-l x2
practical purpose. Finding 1"' and 2"0 order
Inflation Point in van der derivative and equating it to zero
Waals'Equation as we are working out equations at
a point of inflation we get;
Van der Waals'equation (7)
being cubic it turns complicated as dynvittdst2w
we seek roots. Some mathematical ............_:v-- ---t*-,, -7"(10)
modeling packages facilitates in dx-"
generating roots but yet redundant-
' not practical for use. d'y r./..1Jr t 3w
=^ =7.(11)
Now we shall look for d^, '-(.r_ry
inflation point arriving in plot of

]. : ;
lJ :U3
Fig. 3: A ptot of - ; depicting inflation at x=3.
 L62
S W ANWANtr

inflation Point Hence it is

Last two equations can be
simultaneouslY Processed to ind.ependent of f and ru'
eliminate Parameters t and u and One maY Press following
finally find the x-value of point of command in MaPle 14 to see the
inflation. A simple processing gives same graPh and maY PlaY with
,t-- -
2
.J.
various values of the Parameters f
- and ta to notice that inflation is '
Fig.3rePresentsaPlot independent of which was
Point at
showing an inflation analyticallY noticed'
preferred values of parameters t- 1 ' 5 Conclusion
and w=5.05. The inflation is Roots of equation and its
irrespective of the parameters I and
ru. However a visualization effect is
type (real/comPlex) dePend u-Pon
prominent for these Preferred parameters t and u in reduced form
of van der wdals equation' However,
values. In rest cases it is Present
but visual effects seems to be inflation Point is irresPective of
U sing
masked. Reader must have noticed the se Parameters '
from the analYtical aPProach of mathematical modeling tool MaPle
eliminating t and tu Yields the 14 has been used for equation
manipulation and visualization'

I
pJ'la fs*ro,-oo,lirr*rr*u,r*u F&J I$ rnl,*irr:jrpfot '
I
'::r * $ ".J, l*f'ttt's* l"r.:'ll I l.r {}..1t}. n'* t}..ltl
I
i

References
PaulJ. Gans V25.0651 - Physicai Chemistry I' September'
1993

S W Anwane vol 25 No.9 - bulletin of Indian Association

of Phgsics
Teachers Nov 2008.
Andre Heck 2"0 Edition Introduction to Maple 1996
Acknowledgement
TheauthorgratefullyacknowledgeUniversityGrantsCommission'
Project No'F'47-
New Delhi for linan-cial assistance under Minor Research
1233/0e(wRo).
VAN DER WAALS EQUATION: AN INTERACTIVE APPROACH 163

Appendix 1
> y::o'i+b.x*c
sr'r6ve fi:r'x
*****+ a? + bx + c

ar

ll.:+ -t,+Ji-+'" ll---,L b+'[F-q,,

[t'* 2 , i'l': ---- , --]t
11

oi +bi *cx*rt
,,:o.i+b.;*c.x*d
'
't,{.1[r"* r x
%_+

ii,t -

ljr*4li4tea*
ri I
Esrr**.r
li

* r; ,'il#T-: d;i;o*; ;',ii?.i.";:;;, i"

,, .$ u- ly *' .t.r
- ,u'-l- j'l i",rur*^ t$'ar^ Bst*.r:
"J;tr"- lT;I--;at-;';;;;;r;;
'i ,,1 !
t.i "jl-= "*ilon*.
r
". :risr- $oi

.,%.q.i.l
, !iri lt#* Jyd * 3+s*c, itl " *t,! l" '

r ri', j"
- !l, ,i*--
t
*"jllirsh"* !{}nr* B*} +*rffff)1371Gaf-T'xr7T6l}
-1
'*
4 - *r"-r
+, [ - 1,&$ i w**-
t".
ri))rr * $e;:
i.

* l:," l-r ;j' - .l t; f * .j.t b*t q frl * .l)t,,,it 1' "

i*

11.r'
",u,r+. - | ;. i;1 lr* kx * t{}E:.r * t,l .r" ts,r; b:t ::;p;};;;;;g;-i;;
I

"l;tl I
l:,,r'
I ;.; 1)t.:* i(!/ . 6fl'
'r j '4
 L64
S W ANWANE

,li.$
+ *; rSd - $+;u*u + bl # * t3r# I
"'{:;,#'*,

, .-r, l- i -"tehor + &!*: + lJcd

* ir
i, ii
'" I :,* Li\tll
.rJr
l:ru*"* !fiBr*$d + t: uiH aT;;r.
"

LE
*
"'*
J:
- ; t1 ) I {t*1"- tfr$r 'tir:i

* 1:1.'t: $i * 1& d* "\-rbcr * 3l f * llr*f l

+ftr'trf. {;{r j,*s*-t #?{?:l;

* t*
' l.r l#. l.v
7
ilito*
:;:
bt:t-" t*ae ^'*d l

rl i
il.

Appendix 2
a simPle cubic
Here, we disPlaY respectively. Its 2"u order derivative
function that one deals in has negative value at maxima and
preliminary mathematics. Along positive at minima.
with its 1"'and 2"" order derivative 7 S::i++.]*2.x-r
is also depicted. The 1"t order
derivative vanishes at maxima and f+qi*2x-l
(*'))'':-o')
F r. +m1 r.= + - +k)''"(i'*'*

, ,r1'
;'l -.---.

-3*r 13
It posses three real roots that appears as; x = -1, -Y = -=-. Numerical

set that can be verified in the graph are; {"-1, -3'3*2,0'3*2}'

 L62
S W ANWANE

Last two equations can be inflation Point Hence it is

simultaneouslY Processed to independent of t and ttt.
eliminate Parameters t and w ar.d One maY Press following
finally find the x-value of point of command in MaPle 14 to see the
inflation. A simple processing gives same graPh and maY PlaY with
various values of the Parameters f
and tu to notice that inflation is ,

Fig.3rePresentsaPlot independent of which was

Point at
showing an inflation analyticallY noticed.
preferred values of parameters t- 1 ' 5 Conclusion
and w=5'05. The inflation is Roots of equation and its
irrespective of the parameters I and
u.,. However a visualization effect is
type (real/comPlex) dePend uPon
prominent for these Preferred parameters t and tt in reduced form
of van der waals equation' However,
values. In rest cases it is Present
but visual effects seems to be inflation Point is irresPective of
these Parameters. Using
masked. Reader must have noticed
from the analYtical aPProach of mathematical mod'eling tool Maple
eliminating t and tu Yields the 14 has been used for equation
manipulation and visualization'

F { q' ! s,,, }r /(r lsrrr r,*ficiri,l,,r'

r rr-o r,,,,.uPono,,n, |
t
,* -- 5 /il&El"v *, l.r. I I l, , *' {} ..1{}, t't'' '* {.}
".5, J, tr,
t
,s

References
Paul J. Gans V25.0651 - Physical Chemistry I'
September' 1993
SWAnwaneVol25No.g-bulletinoflndianAssociationofPhgsics
Teachers Nov 2008.
Andre Heck 2"o Edition Introduction to Maple 1996
Acknowledgement
TheauthorgratefullyacknowledgeUniversityGrantsCommission,
Project No'F'47-
New Delhi for finaricial ass"istance und& Minor Research
12s3l0e(wRo).