CHAPTdR 7

FUNCTIONAL
RELATIoNSHIPS

o[ anothcr.]"*olt !l.t:'
A variablc (/) is said to bc a function ln
valucs of 7' 'r":
various valucs of x. it i'
p"JUf t ro cstablish corrcsponding
by writing:
*c dtscribc this situation
mathcmaticat 'yrnUoti'-'

t = IGl.
valucs is rcfcrrcd to as
u'c frrst assign numcrical
Thc variablc (r) to which
rhc indcpcnd.r,,,..i.uil",i. r,i".i..i"uie (y) is callcd thc dcpcndcnt
variablc- For
simplc functional rclationships'
Tabtc 7.1 lists a [cr' rclativcly by substituting x = 0' l' 2'
cach funcrion, wc givc ,t. *lr.t';;;..,.i",.a
and 3 in thc corrcsponding cquatton'

. if r -'''
thcnT -....
.. ifr -
.thcn; -.,.
.' dt:..
.thcny -..
. ifr --
thcnl - . . ..-.j-.iril.
l,;:: :'Ji,'ljik'j ::.;1'+l
j. :.ri,,'lr!'j { :':r}

80
-:1
 fUNCT'ONAT 8ETAI'ON5H'PS 8I
Equarions rcla(ing ona variablc to anorhcr usually includc onc or .norc
numbcrs. In thc funcrion./ 3:,. thc numbcr 3 appcars; in the funcrion
-
| - -
8x 3. wc havc two numbcrs, 8 and Thcsc numbcrs arc oftcn
-3.
rclcrrcd to as constants, sincc thcy arc thc samc for all'valucs of r and.;r-

7.1 FUNCTTONAL RETATIONSHIPS IN GENERAL

CHEMISTRY
Pcrhaps thc simplcst typc of functional rclationship is that in which 7
is dirccdy proportional to r. Thc first rclation lisrcd in Tablc 7.t (; -
3x) is an cxamplc of a dircct proportionality. Thc gcncral cquarion is:

t-at (7.t)

whcrc a is a constan!. An cxamplc o[ a dircct proportionaliry lhat wc cn-

countcr in gcncral chcmistry is that rclating thc ratc of dccomposition of
thc gascous compound. N1O1, to its conccntration:

Thc.quanrity t appcaring in this cquation is callcd rha ratc consranr. A( a

gitcn jcmpclaturc; it has a fixcd vatuc wtrich could bc lound by mcasuring
thc fatcof rcaction at onc particularconccnaration of N101, i.c.:

t = ratc/(conc. NrOr)
Arroihcr typc of functional rclationship which ariscs lrcqucntly in
gcncral chcmistry is an invcrsc propo.rtionality. Thc rhird rclarion listcd
in Tablc 7.1 O - 4/r) is o[ this typc. In gencral, 7 is invcrscly propor-
tional to r if:
d
t-i (7.2)

whcrc a, once again, is a constanr. Thc concentrations o[ H' and OH - in

aqucour solution at 25'C arc invcrscly rclatcd ro cach othcr. In this casc,
thc constant, oftcn rcfcrrcd lo as thc ionization cons(an( of warcr, has thc
numcricalvaluc 1.0 x l0-rt.

(conc.H')-##
Thc functional relationship which wc will considcr mosr cxrcnsivciy in
this chaptcr is thc lincar function, which has thc gcncral lorm: '

t-at+l (7.31
82 CHAPTER 7

whcrc d and , arc both constants- The phrasc. "lincar: funttion" is used
bccausc a straight linc is obtaincd when 7 is plottcd against r (see Scction
7.2). Thc rclationship:

l-ox
with e - 0.
is, of courcc, a spcciat casc of a lincar function.
Onc of thc fundamcntal cquations of thcrmodynemics,. lhc so<allcd
Gibbs-Hclmholtz cquarion, can bc considcrcd as a tincar function rctating
rhc frcc cncrgy changc, AG, to thc absolurc tempcraturc, I:

Lc-LH-ras (7.4)
a

The quantitics AH and AS appcaring in rhis cqtration are "constants" in

rhe scnsc that they do not vary, at lcast to a 6rst approximation. with rem-
pcraturc. Thcsc quanrirics arc rcfcrrcd to as thc cnthalpy changc and
cntropy change; rcsPcctivclY.

7,1 Using Equarion ?.4, dctccminc:

Exornplc
. a. ACar 400'K for a reaction for which AI{ = 61.0 kcal and
AS - 0.020 kcal/'K.
b. AGar 500'K for a rcaction for which AH = -32.0 kcal
and AG - -20.0 kcal at 300'K.

Solution
a. AG - 6l.0kcal - 400'K(0.020kca1/'K) - 53.0kcal.
b. Onc way to solvc this problcm is to 6rst calculatc AS by
applying Equarion 7.4 at 300'K, and thcn usc this value
to calculate AG at 500'K.
At300'K: -20.0kcal - -32.0kcal - 3d0'K(A.t)
AS = -12-0kcal/300'K = -0.040kca|/'K
At500'K: - s00'K(-o.o4o kcal/'K)
^" - :il.[tcal

Anothcr rypc of functional rclationship which turns up rcpcatcdly in

gcncrat chcmistry has thc form:

rosT= o.s)
?*t
 fUNCITONAI'RETAI'ONSH'PS 83

An cxamplc is thc rclationship bctwccn thc vapor prcssurc of a liquid ( P)

and thc ebsolutc tcmpcraturc (I):

ros r-ffi+a (7.6)

whcrc Aff-, is thc molar hcat of vaporization (cal/molc) and R is thc gas
. constaat (1.99 cal/molc 'K). Thc functiooal rclationship bctwccn P and
Iis oftcn crprcsscd in tcrms o["6nat" and "initial" statcs. If wc rppty
Equation'7.6 at two diffcrcnt tcmpcraturcs, 7r and Ir:

' " ' togPl-

ffi*,
losPs - #,*,
. subrractins: ros& - rosff
r #,' #,- *t+ +J
.:-. .-...

:;''tri;-^*W; (7.7)

Eromplc 7.2 Thc vapor prcssurc of watcr at 298'K is 21.6 mm

Hg; its hcat of vaporizarion is 10,500 calr/molc. Calculatc:
a. Thc'vaporgcssurc of riatcr atf l0'K.
b. Thc tcmpcra(urc at which watcr has a vapor orcssurc.of
30.0 mm Hg.

Solulion.

Pt to.soo lrto zse] -

-a (2.30)(l.ee) L(rl0)(2e8)J

- 0.298

bs
*, - o.zea

Pt
Taking antilogs:
23-6
1.99; h = 17.0 mm Hg
84 CH^PTER 7

10.500 (72 - 2e8)

b. bsH- (2.30)(r.99) 29872
(i-t :298)
1.477t - 1.3729 - 7.70
Tt

Ccrtain of thc quantitics that wc dcal with in gcncral chcmistry arc a

lunction of morc than onc variablc. A [amitiar cxamptc is rhc volumc, /,
o[ an idcal gas, which is a function of thc numbcr o[ molcs, T , thc tcmPcra'
turc, I, and thc Prcssurc, P. '

,-ry (it - gas law constant - O.O82l lit atm/molc'K) (7'8)

If wc specify tbc numcricat valucs of two o[thc variablcs; it is possiblc

to
bcrwccn thc othcr two variablcs' For examplc, if,w'c
obrain a rclationship
arc dcaling with onc molc ofan ideal gas at onc atmosphcrc Prcssurc: .

I molc (0.062t lit atm/molc'K) I lit -

,,
' latm
= 0.0g21 .i.,
and -
Again, for two molcs of gias at 3OO'K, the rclationship between votume
prcssurc is:

.. :--.-__p
(? molcs)(0.0621 lir atm/molc'K)(300'K) 49.3 lit atm
I
Throughout this scction' wc havc rcfcrrcd to various "constants"
which arc uscd ro cxPrcss functional rclationships- Frcquently, thcsc
constants havc units, as is thc casc with thc gas law constant uscd in Equa-
tions ?.6 and 7.8:

1.99 cal 0.082! lit atm

^^ -;il.iffi-;'t.x
Hcrc, wc must bc carcful to cxPrcss R in units i'vhich arc consistcnt with
thosc uscC in othcr rcrms appcaring in thc cquation' In Equation ?'6'
whcrc AHis givcn in callnoic, rt should bc cxprcsscd as l'99 callmolc' ln
Equation ?.8,-it t/is givcn io litcr and Pin almo$hetct, wc should usc R -
0.0821 ln ahlmolc'K.
ccrrain of the ..constants" that wc work with in gcncral chcmistry arc
fUNCTIO'TAI. 8EI,AIIONSH'P5 85

thc4sclvcs functions o[ othcc quantidcs which do not appcar in thc cqua'

tion. An cxample is the t"t" *, for rhc dccomposirion o[ NrOr :
"ontt"nt,
ratcof dccomposition'of NrOl - t (conc' NrOr)

Thcnurncricalvaluco[ldcpcnds lpon rhc rcmpcra(urc at which thc ratc

is mcasurcd. At 400'K, t is 1.3/sci; at 500'K. t is 170,/scc' If
wc writc
thc cxplicit cquation:

170 (conc. NrOr)

,tc-.-_.F

*..,.::.. tu,'..ion"l rclarionshi p is limitcd to o nc

ffi::.#H|t..**
EXERCISES

''1. Fora ctnain rcaction, Aff is +21'0 kcal and lG is +17'0 kcal at
300'K. Using Equation 7-4, calculatc:
a. AS
' b. 'AGat 500'K
c- Iat which AG - 0
'2: Thi .q"iiu;r. c'o'nriint- for a. riactioh. i(' varics wiih rcmpera'
-'
turi, I; eiccordirig t6 thc iclatiori:
Kz AH lT, - Tt\
.tosE
z.n\rn I
whcrc Affis in thc cnthalpy changc in cal/molc, fl is thc gas law constan(
(1.99 cat/molc). For a ccrtain rcaction, K is l'0 at 300'K' Calculatc l(
at 400:KitAIIis:
a.0
b. +1.00 x l0'cal/molc
c. -1.00 x t0'cal/molc
3. At 271'K and one atmosphere Prcssure. onc molc o[ an idcal gas
occupi6 22.{ litcrs.
a. Using Equation ?.8, cvaluatc it in lit atm/molc 'K'
b. Givcn that I lit atm - ?4.? cal. calculatc rQ in cal/molc 'K'

7.2 GRAPHS OF FUNCTIONS

Funoional rclationships bctwccn twb variablcs can always bc rcprc'
scntcd graphically. Ordinarily, wc usc th. ,crtlcal fot tlrc dcpendcnt
"tit
86 CHAPTER 7

variablc, r, and rhc horizontal axis for the indcpcndcnt variabtc, x. If wc

wish to graph rhc functioni

, - 2'5r + 3-0
in the rcgion bcrwccn .r - 0 and r- 5, wc might firsr calculatc y tor x -
0, 1.2, 3,4, and 5:

/ 3.0 5.5 8-0 t 0.5 r 3,0 15.5

x 0r2 345
and thcn locatc cach of rhcsc point; on thc graph. Thc 6rst point (r - 0,
, - 3.0) is locatcd on thc)axis (r = 0). thrcc units abovc thc origin (.7 -
3.0). Thc sccond point (r - l,y - 5,5) is located by moving out onc unit
horizontally from thc origin (x - l) and thcn moving 5.5 units vcnically
(,1 - 5.5). Thc graph which rcsults whcn thc six points locatcd in this
manncr arc conncctcd is shown in Figurc 7.1.
Wc norc that thc plot of thc function:

j-2.5r+3.0
is a straig ht Iinc whicli cuts thc , axis at 3.0. Thc slopc ol this line may bc
lound by dividing the diffcrcncc bctwcen final and initial values of1 by thc
diffcrcncc bctwccn thc corrcsponding x values-
 fUNCITONA[ NEI^I'ONSH'PS 87
'Ar li.s 3.0
-
sloPc-'z'-=-;:-2.5
Wcconcludc rhat for this function, thc rlopc is 2.5 and thc,;r intercept
(thc raluc of.7 whcn.r - 0) is 3.0. ln gencral, wc can say that thc graph ot
thc cguation:

1-ax*b
is e streigLt linc wirh r slope of e and en intcrccpt of b. To shonr that
this istfic casc, we first lct r- 0, obtaining:

fo-'o(O)+A; h-b
whcn: - l: Jt - a * b

A1 tt-t\ k+bl-b
uubtradrng: stopc r -,
A, -', _it TO-
. Many o[ thc functions tha( wc work with in gcncral chcmistry givc
plots which iic smooth curvcs raihcr than straight lincs. Examplcs inclrrdc
Equarions 7.2 {y * a/x) and'7.3 (log7 - -.llx + 8), which arc plottcd
in Figur-c 7.2.

320
T
(bt
flGUnETr. lolt - ol+ (o - lol

. Flber--i*t
(^-240o.t-9J01
 CHA?TER 7

Exomple 7.3 . f,onstruct a graph of the function:

losP
,T = -2fo + s'lo

in thc rcgion bctwccn f = 3OO and I = 340.

Solution In ordcr to construct thc graph, it will bc ncccssary to
1es31s 56vcral points within this rangc. To do rhis, wc migli,t calcu-
latc valucs of Par l0' intcrvals betwccn 3fi) and 340'K:

r - 3oO; logP = -5'#o'* 9.30 = l.3o; P - 20; (2 sig.

6s')
?r - 3t0; logP =
*# * e.3o = 1.56; P-36

r - 32oi logP =
# *9-30 - 1.80; P.= 63

T - 370; los f..= -3rf9 * e.30 = 2.03; P=ll0

:..
r : r4o;' rosP- -ii8o *o:o - z.ic; P=170

Thcse poiots arc plottcd and conncctcd by thc smooth curve.

shown at thc righr of Figurc 7.2.

Frcqucnrll'. as in Examptc 7.3, wc arc askcd to plor a graph through a

scrics of points corrcsponding ro succcssivc valucs of x and 7. In drawing
graphs ro rcprcscnt lunctional rclationships, wc attemPl to sprced thc
gr"ph or.r as vridc an arca of thc gnph PaPcr as possible' This oftcn
icquircs that wc assign diffcrcnt valucs to thc inrcrvals along thc lwc axcs'
Supposc. for cxa.mplc, r^'c arc askcd ro plot thc data: :'

I 0t0 20 30 40 50

I 0l 2345
If we wcrc to insist that thc samc intcrval rcPrcscnt onc unit'along
both axcs, wc would gcr thc straighr tinc shown in Fig. ?.3a- This graph
would bc rathcr difficulr lo rcad, sincc it ncarly coincidcs with thc ;l axis'
It would bc bcttcr to lct an intervat'alon( thc y axis rcPrcscnt l0 units, ai
FUNCT'ONAI R€I.AT'ONSH'PS 89

fIGUIC

comparcd to I unit along thc x axis, thcrcby obtaining thc srraight line
shown in Figurc 7.3b.
. Following this samc principlc. it is oftcn inadvisablc to lct thc intcr-
scctiori o[rhe two axcs rcPrcscnt the point (0,0)- Supposc wc wcrc askcd to
plor thc data:

, 200 205 210 213 220

r 100 l0l 102 I0l 104

It woutd bc unrcasonablc, to say thc. lcast, tostail our graph at .;r - 0, r -

0. If wc did, wc wguld gcr thc ncarly invisiblc linc shown in Figurc 7.4a'
The ipacc auaitablc to us could bc utilizcd much morc cffcctivcly by start-
'ing'ar rht towcr lcft with 7 = 2OO, x - 100'

100
(:)
RGUTE 7.{.
 O{APTER 7

Exomplc 7-4 Thc prcssure of a samplc of gas maintained at

conslent volume is mcasurcd at a scrics of tcmpcraturcs:

P(mm Hg) 90 93 96 99 102

rrK) 300 3t0 120 330 340

Plor rhisdara (Pon thc vcnical axis, Ion thc horizontal aris) on
rhc graph papcr bclow (Figurc 7.5)-

Solution Wc must a."ia. vrn"t valucs to assign to thc divisions

atong thc rwo axcs. Lct us 6rsr considcr thc x axis. Wc notc that
thcrc arc 20 spaces along thc x axis; thc lcmP€rature rangc to bc
covcrcd is a0'K (340'K - 300'K - 40'K). It would sccm rca-
sonablc to tct onc spacc rcprcscnt 2'K. Sraning with 300'K ar
thc lar lcft, iucccss.ivc divisions bccomc:

: . 300.302,104,306,30q, 310, ' ' '336,338' 340

,J
Along rhc ) axis, we havc 15 spaccs which must iover the
rangc bcrwecn 90 and 102 mm Hg, i.c., t2 mm Hg. To use the

flcut€ 7.5. Plol ol prorurc of gor :ooplc (mm Hg) n tcnPctolerc Cq'
.fUNCI'ONAI, REI.AIIONSH'PS 9I
. cntire distancc, wc could lct one spaccreprcscnt

12 mm Hg/|5 - 0.80 mm Hg

ln practicc, this choice would bc awkward, bctausc lucccssivc di-

visions would not corcspond to intcgers'That is' wt would havc :

90.0, 90.8,91.6, 92.,(. g3.2, -. - - ro6.+. 101.2. 102-0

h would bc simplcr to lct onc spacc along thc .;r axis rcprcscnt I
mm Hg. If wc start at thc bottom with 90 mm Hg. succcssivc
divisions bccomc:

90,91,92.91, . - .99, 100, l0l, 102

Using 2'K and I mm Hg as divisions, thc data is plottcd in

Figurc 7-5. Noticc that onty a rclativcly small rcgion ncar thc
top of thc papcr is not uscd.

EXERC'SES .

l. Graph thc following functions, from r - 0 ro r- 5:

a. 1- 6.0t d. logy - 8.O0/t - 5.0O

b- t - t2/, c.I =-1.6r+12.0

c't'2'lox2 t.2l -lr-9
2. Whichof thc functions in nurhbcr (l) arc lincar? For cach lincar
function, givc thc slopc and intcrccpt.
3. Graph thc following scts of data. drawing a smooth curvc through
thc points:

a.7 '12.8 13.2 -6

l7 20.0 22-4
r0l 234
b. 1 6.00 5.OO 4.29 ).75
r 0.50 0.60 0.70 0.80
c. / 10.0 100 450 t300 3200

.. 20ri 250 300 t50 400

 ,t
o2 CHAPTER 7

7.3 LINEAR FUNCTIONS

As pointcd our iarlicr, scvcral functions that we dcal with in gcneral
chcmisrry arc o[ thc form:

,-ax+b
x. lvlany morc complcx
and yicld a srraight line when.;r is ptorrcd againsr
rclarionships can bc rranslormcd into lincar luncrions by a simpte change
in variablcs. Considcr, lor cxamplc, thc funaion:

t'o/r
If wc plor, vs.r, wc g.t a hyp..biota rathcr than a straight line (Figure
7.2a). Howcvcr. i[ wc plot .y vs lf x, we gcr5a srraighr linc with a stopc of
a (Figurc 7.6a). ln orhcr wbrds, by changing the indcpcndenr variabtc
from r to I / x, wc transform a hypcrbolic into a tinear funcrion.
Anothcrfunctional rclarionship which is rcadily'convcrted ro a tincar
funcrion is:
.. .i. . - .. ,
_/
logr-:+B
.

lf wc choosc logl and l/r ro bc our variablcs rathcr rhan l and x, wc

obrain a lincar [uncrion (Figurc 7.6b).

log P

0.8
1lx 1n
(a) (b)
FIGURE 7.6.

or, _ ,. (*)
(blroeP - -r.* (1) * rr.
fUNCIIONAI, IEI.AI'ONSH'PS 93

' Convcning a morc comPlcx functional rclationship into a lincar func'

tibn has an obiio,rs advantagc; it grcatly lacitiratcs thc proccsscs of intcr-
polation and cxtrapolation- Supposc' [or cxamplc. rhat wc wishcd to usc
.hgur.7.2a to 6nd y whcn r - 0.5- This would bc'rarhcr difficult to do.
siicc it would ."q.rir" c.*rcnding thc curvc in a rcgion whcrc thc rlopc is
changing rapidly, on thc othcr hand, it woutd bc rclativcl.n casy to cxtcnd
the straight linc in Figurc.7.6a to End that:

' ,-20whcnr-0.5 (l/r-2-0)

Trensforming complcx funcrions ro'lir,ci. functionr has aoothcr. lcsr

obvious adrantage. It oftcn happcns that thc slopc (and somciimes lhe
intcrccpt) of .tbc.rcsultant srraighr linc has dirccr ph1'sical signincance.
Considcr, for cxamplc, the rclationship bctwccn thc vapor pressure o[ a
liquid and thc absolutc tcmPcraturc:

rogP-
tr*, (7.e)

ItlogPis plottcd vs llT,as in Figurc 7-6b:

slopc - -.{ (7.r0)

Compiring Equations 7.6 and 7.9. wc scc that:

A-.# (7.1 r )

From Equations 7.10 and 7.11. wc dcducc rhat thc hcar o[vaporization o[ a
liquidcah bc obtaincd by ta.king thc slopc o[ a plot of log P vs l/7' That
ii:
LH,.e - -2.38(slope) (7.t21

Sincc the slopc and thc intcrccpt o[ a linear function are oftcn physi-
catly mcaningful quantitics, it bchoovcs us to considcr ralher carcfully how
thcsc quantirics can bcst bc dctcrmincd accuratcly-' Thc problcm is csscn-
tiallyas follows: Supposc wc havc obtaincd data in thc laboratory which
can bc 6trcd, pcrhaps by transforming variablcs, to a lincar funcrion' How
can r,4 bcst use that data to dctcrmine (hc constants in thc cquation:

1=ax*b
whcrc o is thc slopc and 6 is rhc intcrccpt ?
94 ) CHAPTER 7

Thc proccdurc which we follow to obtain the constants a and 6 de-

pcnds upoir how much data wc havc availablc- Wc can distinguish two
dilTcrcnt cascs.
basc t. II only lwo points arc aooihbk,.ytc procced as follows: Usin$ thc
subscript r to rcfcr to thc second point and I ro thc 6rst point:

,2_arr*6 o.r3)
1r-o\*b o.t1)

Subtracting: )t - Jr - a(r1 - rs)

of:a-a-+
h-1I 6l ,
rl-rl Ar

Having calcularcd a, 0 is rcadily obtaincd by substituting for a in onc of thc

simulta ncous cquations, 7. I 3 or 7. 14.

Eromple 7.5 Considcr thc cquition:

- AG=5ff-7-AS (r=-A5, b=AH) .

:

If AG is found ro bc 8.4 kcal'ii 300'K, and 10.8 kcal at .400lK; 'cal-

'

culare AHand AS-

Solutioh
(ACr--
AG") -2.4 kcal
A.! = : E
-a - -'-:=T, - T, - -0.024kca1/'K
100:K

To obrain AH, wc apply the eguation:

- AG = AH - I A.l at
100'K:
8.4 kcal = LH - 300'K(-0.024 kcal/'K)
AH = 8.4kcal - ?.2kcal - l.2kcal

Clcarly, catcularing rhc vatucs o[a and l, from only two dara'points is,
at bcsr, a risky busincss. If cithcr of rhc points happcns to bc scriously in
crror, lhc valucs that wc gcr for thc slopc and intcrccpt will bc highly
unrcliablc.
Casc 2. Il thtcc or morc poinb orc availablc, thc constants a and D can bc
dcrcrmincd by graphing thc dara, dr.awing thc "bcstt' straight linc through
the poinrs, and mcasuring-thc slopc and intcrccpt.
FUNCT'ONAI. REI,AI'ONSH'PS 93
In following this proccdurc, it is rarciy possiblc to draw a itraight line
which passcs crorrlT through all of rhc points. At bcst, somc o[ rhc poinrs
will be abovc thc linc and somc.witl bc bclow it, What we a((empt ro do it
to draw rhc linc in such a way that wc havc about as many points abowc thc
tinc as bclow. Morc cxactly, wc istimatc visually rhe posirion o[ rhe linc
such that thc sum of rhc distanccs of poinrs aborc it will bc cqual to rhc
sum of thc distanccs of points bclow thc linc- A transparcnt plasric
straighicdgc, trianglc, or nrlcr should bc uscd, so rhat rvc can scc all thc
points whilc we arc trying to dccidc whcrc to draw rhe line.

Eromplc 7.6 Lct us supposc that thc data givcn in Examplc

has bccn cxtcndcd ro givc AGat four difrcrcnt tcmpcrarurcs:

AG 4.4 kcal 6.8 kcal 8.4 kcal 10.8 kcal

T r00'K 200'K 300'K 400'K

Using a graphical mcthod, dctcrminc thc constants AII and AS in

thc cquation:

AG.AH-rA.'
Solution .ln Figurc 7.7, wc havc plottcd AG vs l-: rhc lour data
points arc showl 3s small circlcs. Wc havc attcmptcd ro draw thc
"bcst" straight linc rhrough thcsc points. Noticc rhat it docs nor
pass cxacrly through thc ccntcr of any point. Thc points at 300'K
and 100'K lalt slightly bclow thc linc, whilc rhosi at 400'K. and
200'Karc slightly abovc thc linc. k appcars that rhc sums o[ rhc
distanccs abovc and bclow thc tinc arc about cqual-
. Thcintcrccpt of thc linc wc havc drawn is 2.6 Lcal. Thc slopc
can be found from rhc valucs o[ AG and I it
rhe crids of rhc linc :

.
stopc - e%tm-
400.
- o.o2o kcat,/.K

We dcducc that: Afil - *2.6 kcal

AS- -tloP. - -0.020kca!/'K
It is intcrcsting to comparc thcsc valucs with thosc calcularcd
in Examplc 7-5 (AH - +t.2 kcat; A.t = -0.024 kcal/'K).
Clcarly, by obtaining rwo morc poinrs, wc havc considerably re-
viscd our cstimatc of thc intcrccpt and slopc.
06 CHAPTER 7

AG
(kcal)

100 200 . 300

TTK)
,lGUtE 7.7. Rclolion bclwccn AG ond Ir AG - +2.6 + 0.020L

. Frtquciltlf, cxperimcntaf data" cvcn though thcy crr,. in.principte bc

hrtcd to. lirr... function, show sufficicnt scattcr to rnakc it difficult to dc'
cide how ro draw a straight tinc through the scvcral points. Onc way to
.handlc this situarion is to usc a statistical approach hnown as thc mcthod.
of least squircs. Without attcmpting to justity this mcthod mathcmati'
catly, wc shall simply statc, without proof, that it gives us thc equation o[
rhc straight tinc rhrough rhc data points which minimizes thc standard
dcviation (Chiprcr lt) of 'rhc obscrvcd I valucs- Thc mcthod of lcast
sguarcs rclls usihar, in this scnsc; thc "best" valucs of the constants a and
e arc:
, 21Dx - a}y (7.1s)
a=--
),x L, - ntJx

LJ'
2wDx - Zt2x2 (7.16)
Er 2x - nDx'
whcrc: lr = no. ofpoints
Z, - r, +12 + !t+ " " " E sumofatlrhc.;rvalucs
2r = rr + 12 + xr * . . sum of all the: valucs

Z1x = ytt I *rrr, +' "

Ttxz
E sumofthc.lxproducts
I,x2 - xtz + ri + ,i + sum oi thc squarcs of thc x vatues
 97
fUNCIIONAI. NEIAIIONSHIPS

. Thc application of rhis mcthod ro a quitc simplc sct of data points is

itiunr"t.d in Example 7-7. It should bc pointcd ou( that thc tcdious a rirh-
bc climiriatcd by
mctic invglvcd whcn -c havc a largc numbcr of points can
using a .o-p,rtcr, which is cmploycd routincly to carrv out lcast'squarcs
calcutations (scc ChaPtcr l2)-

Excmple 7.7 Apply thc mcthod o[ lcast squarcs to thc data in

ixamplc 7.6 t" nii it . constants in thc lincar cquation:
6.G-3,H-fi\.t

Solulion Wc 6rst comPitc a tabtc giving valucs o[7' r' 7r' and 'r2
forcachpoint, rcalizingthat AG' 7,T - x'

I xlx rI
4.4 100 440 1.00 x l0'
6.8 200 1160 4.00 x l0'
8.4 t00 2520 9.00 x l0'
16.00 x l0'
!0-8 _19q
1000
$20
E6{0 30"00 t 16"
10.4

Hcncc: 27 = 3.04 x l0r ; X;r = 8.64 x l0'; n=4

2r = 1.00 x l0'; ,r2 = 1.00 x t0t
Solving fora and 0, using Equations 7.li and 7.16:

0.04 x tor)(1.00 x l0') - 4(8.64 x lo')

" = (r.00 r td)(t.00 x lo') - 4(1.00 x lo')
, -0.416 x l0{ = 2.1 x l0-r
-0.200 x t0'
(8-64 x lO')(1.00 x t0') - (3.04 x tor)(3.00 x to')
"=- (l3ox lo')(t.oox l0r) -4(1.00 x 105)
-0.48 x l0r .a.
' -0-20 x l0'
Wc dcdricc that: AH - +2.4 kcal
AS = -a - -0.021 kcal/'K

Notc that thcsc valucs comParc quirc closcly rvirh ihosc calc.ulatcd
by a graphical method in Examplc 7.6 (AH = +2.6 kcal, AS -
-0.020 kcaU'K).
 98 CHAPTER.T

Thc method of lcasr sguarcs is actuaily a much morc f,owcrful tech-

nique rhan rhis rimplc examplc might impiy. It can bc ,rid.rro. gnty io
6nd thc consrants iri the lincar cquation:

'
'=ot*b
but also rhosc in thc gcncral powcr scrics:

J-o+bx1cx|*dxta...
For a discussion o[ rhc rheory behind thc tcast-squares approach
and its
gcncral applicabiliry. you may wish to consult onc of thc
rcfcrcoccs listcd
in Appcndix t, or cirhcr of rhc lofiowing sourccs: H. W. Salzbcrg,
J. I.
Morrov". and S. R- cohcn: Loboratoly coirtc in phyriear chcmistry. e"Iii-i"
Press, Ncw York. t966, pp.23-21. I. Klotzi Chcnicat
Tiermo$nanics.
W. A. Bcnjamin, Inc., Ncw York, 1964, pp. ZS-27.

EXERC'SES

l. Transformcach of the following into a lihtar lunction by an ap-

propriatc cha nge of variables :
a- ,'-6xr+l d. log.1r - atogx
b. 1-3/x-4 c. !-x2-2t+1.
t. log.;, - a12 f. 1-12+3r+l
2. Assuming rhar 7 is a.linear funcrion of r, dcterminc thc consranrs
oaod bit:
a. 1= Owhcnr - 0and.y = 3whcnr = 2
b. I = Owhcnx= 3and1 = gq,hcnr-4
c. 1 - 4whcnr - 2andy = -2rvhcnx 5
3. Assuming that thc data points: =

, 5.0 7.8 10.8 14.0 r 6.8 t 9.8

r 1.0 2.0 3-0 4.0 5.0 6.0
can be 6tted rorhc cguarionr'l = o, + 6, 6nd aand 6 by:
, a. A graphical merhod.
b. Thc mcthod of lcast sguarcs.

: ''...",:.'.:-..::.1,:-''."."-."i-:.?:i,j.::r...,:l:.:1lii.;:i11..,1-.::.i,I}f,tilEtr

PROBLEMS
7.1 For the rcacrion:

So2(g) + Or(g)
2
- 2 SOr(g)