DebyeHuckel

Debye HuckelTheory
Theory
 Ionicatmosphere
o c at osp e e
Solutionsofelectrolytesarenonidealatrelatively
low concentrations. The activities of ions in solution
lowconcentrations.Theactivitiesofionsinsolution
isrelativelylargecomparedtoneutralcompounds.
IonsinteractthroughaCoulombic potentialthat
variesas1/r(risthedistancebetweenions).Neutral
i 1/ ( i th di t b t i ) N t l
solutesinteractthroughLondondispersionforces
thatvaryas1/r6.Thegreaterthechargeontheions
thelargerthedeviationsfromideality.Forexample,
permoleofCaCl2 dissolvedthedeviationfromideal
behavior is larger than for NaCl duetothe2+charge
behaviorislargerthanforNaCl due to the 2+ charge
ofcalciumion.Theseconsiderationsleadtothe
conceptofanionicatmosphere.
 Ionicsolutions
o c so ut o s
WeconsiderageneralsaltC+A,which
dissociates into n+ cations andn
dissociatesinton and n anionsper
anions per
formulaunit

C+A (s) +Cz+ (aq)+ +Az (aq)

Where +z++
Where + z =0byelectroneutrality.We
= 0 by electroneutrality We
writethechemicalpotentialofthesaltinterms
ofthechemicalpotentialsofitsconstituentions
accordingto
2=++ +
wherethesubscript2referstotheionicsolute.
 Ionicsolutions
o c so ut o s
Asforneutralsoluteswehave
2=
= 2o +RTln
+ RT ln a2
butforionicsoluteswehavethat
+=
+o +RTln
+ RT ln a+
and
=
o +RTln a .
+ ln a++ ln a =ln a2
whichimpliesthata22 =a+n+ an
Wecanusethisdevelopmentofintroducethe
meanionicactivity.
a n=a+n+ an
n where
h =++.
 Ionicsolutions
o c so ut o s
Wecannotdefinetheactivitycoefficients
of individual ions but we can determine the
ofindividualions,butwecandeterminethe
meanactivitycoefficientsbythesamemeans
y
usedtodeterminetheactivitycoefficientsof
othersubstances.Themeanactivity
coefficientsaredefinedbasedonsingleion
activitycoefficients
ti it ffi i t
a+ =m++anda =m
wherem
h + andm
d arethemolalities
h l li i ofthe
f h
individualionsgivenby
m+ =+m andm
and m = m.
m
 Ionicsolutions
o c so ut o s
Inanalogywiththedefinitionofthemean
i i
ionicactivitya
i i wedefineameanionic
d fi i i
molality,m by
m n=m+n+ mn
andameanionicactivitycoefficient,g
y , g byy
n= +n+ n.
Given these definitions we can write
Giventhesedefinitionswecanwrite
a n=m n n
 Activitycoefficient
ct ty coe c e t
Atlowconcentrationsofionicsolutethe
meanactivitycoefficientgoesas
ti it ffi i t
ln = 1.173|z+z|(I c/c ) o 1/2

Hereco is1mol/Landwherez+ andz arethe

chargeofthepositiveandnegativeions
involvedinachemicalreaction.Thisisthe
concentrationinthestandardstate.This
t ti i th t d d t t Thi
standardconcentrationcancelstheunitsof
ionic strength
ionicstrength.
 Ionicstrength
o c st e gt
Theionicstrengthiscalculatedusing:
1 2 2
I c = z+ c + + z c
2
wherez+ andz arethechargeofthepositive
andnegativeions,respectivelyandc+ andc
aretheirconcentrations.Itisimportantto
th i t ti It i i t tt
notethatz+ andz ionsthatmakeupthe
solution are not necessarily the same charge
solutionarenotnecessarilythesamecharge
asthoseinvolvedinthechemicalreaction.In
otherwords,excessionsinsolution
contributetotheionicatmosphere.
OriginoftheDebyeHuckelTheory
g y y
Wheredoesthefactorof1.173come
f
from?In1925DebyeandHuckel
? I 1925 D b dH k l
derivedthefollowingformforthe
activitycoefficientinionicsolutions.
i i ffi i i i i l i
q 2j
ln =
8 0 rkT

ThisexpressionisbasedonCoulomb
This expression is based on Coulombss
lawandontheconceptofaDebye
length 1/
length1/.
 TheconceptofDebyelength
p y g
ThisexpressionisbasedonCoulombslaw
and on the concept of a Debye length 1/
andontheconceptofaDebyelength1/.
TheDebyelengthcanbethoughtofthe
approximate radius of the ionic atmosphere
approximateradiusoftheionicatmosphere
ofanion.Fora11electrolyte
1 = 304 pm
c mol/L
Whentheconcentrationoftheelectrolyteis
When the concentration of the electrolyte is
0.01MtheDebyelengthisapproximately
3000 pm or 3 nm.
3000pmor3nm.
 LimitationsoftheDebyeHuckel
approximation
i ti
Thegeneralformulafor
g is:

2e 2 N A1000(L/m
( 3
)
= I c/mol/L
/ l/L
0 rkT

DebyeHckeltheoryisvalidonlyinthelimit
oflowconcentrations.Thetheorybreaks
downwhentheconcentrationofthe
electrolyteisgreaterthanabout100mM.