L A B O R AT O RY M AN U A L

P H YS I C A L C HE M I S T RY

BY
JR
"
A L B E RT W D AV I SO N
P rofesso r of P hysic al r
Ch emist y

AND

H E N RY S . v an KL OOST E R

Re nsse la er P o lytec hn ic I ns t itu te

NE W Y O RK

W I LE Y s: S ON S , I n c .

C H AP MAN H ALL, Lm rr w
1 922
 P R E FA C E

IN presentin g this m anu al of laborator y ex erci ses in ph y s

i cal chemistr y the authors have bee n prompted b y a three
,

fol d object : fir st to facilitate the tas k of the instructor in

,

handlin g l arge c l asses o f stude n ts beginn in g a course o f practica l

physical chemistr y ; sec o n d t o assist the stude n t in recordin g
,
.

his obser v atio n s in a clear a n d comprehen sive mann er ; an d

third t o present such Quan titative ex ercises as will be partie
,

ul arly desirable in the trai n i n g of stude n ts of e n gi n eerin g .

I n vi ew of the fact that there are as a rule availab l e for

, ,
'

l aborator y w o r k n o t m o re than two an d o n e half hours at a-

t ime it has been found desirable to have the differen t pieces

,

o f apparatus set up beforehan d by the instructor To this .

e n d , each e xperime n t is preceded b y an e x act l ist of the appa

ratus an d chemicals neede d I t is b elieved that this will materi

.

all y ai d the instructor in assemblin g the necessar y equi pment .

At the R ensselaer P olytechn ic I n stitute the la b orat o r y course

,

i mmediate ly follows the c o mpletio n of the theoretical c o urse

in physical chemistry and students are thus prepared to take
,

up the stud y o f a n y exper iment here in liste d I t is therefore

.

found practica l to prepare the equipment f o r o ne o r two u n its

o f each ex ercise before the laborator y course starts and t o shift ,

the studen t successively from o n e experiment t o another In .

thi s wa y an ex cessive amoun t o f preparator y wor k is avoided

, .

M an y of the experimen ts have b een in use in their presen t

form at thi s I n stitute a nd elsewhere fo r a number o f y ears
, , ,

a n d have bee nfou n d to be thoroughly satisfactor y .

Directio n s have b een made as co n cise as possible D e scrip .

ti v e matter perta ining to thermostats polarimeters an d o t her

, ,

iii
iv P RA
E F CE

phy s i ca l measur ing in struments h as p urpo sely been o m i tted ,

sin ce these are adequatel y described elsewhere F or these .

detailed descriptio ns stude n ts are referred to t h e many excel

,

l ent la b oratory manuals q uoted a num b er of which may well ,

be kept o n t h e la b oratory book shelves F or theoretical dis -

.

cuss io ns a nd f o rmul a
,
reference must be had to t h e textb ooks
,

in current usage .

S ome of t h e e xerc i ses given are no t d escri b ed i n the current

m a n uals no r indeed in t h e literatur e
, I t is hoped th at t hese .

co ntri b utio ns may b e found useful elsewhere Th e number .

of e xper ime n ts is lim i ted b ut the y have been caref ull y chosen ,

with the aim of coverin g the whole field of eleme n tary ph y sical
chemistry in a qua nt ita t ive manner s o that t h e student will ,

be e na b led to perform all of the e xperiments prese n ted with ,

out omissio n s in t h e tim e usually allotted to a laboratory

,

co urse of t his ch aracter With t h e e xceptio n of two or three .

e xperim e n ts th e majorit y of these e xercises c an be performed

,

with t h e usual apparatus to b e found in a ny chemi cal la b oratory .

B la nk sheets a nd cross sectio n paper have b een introduced -

in order to mak e the manua l a student no te book as well as a -

laboratory guide .

S
Th e authors tak e th i s oppo rtuni t y t o e xpress the ir apprec i
ation for t h e kindl y criticisms an d t h e man y suggestions received
from Dr F H Getman H i llside Lab orato ry tamford C onn ;
. . .
, , ,

Dr E dward M a c k J r O hio S tate University ; Dr H arry B

S
. . .
.
, ,

Weiser Th e Rice I nstitute ; and Dr J H unt Wil s o n L afayette

,
. .
,

C o ll ege pecial recognitio n shoul d be given to Dr A T L incoln

. . . .
,

of C arlet o n C oll ege u nder whose directio n the lab o ratory course
,

in ph y si ca l chem ist ry was first es ta b lished at thi s I nstitute .

Thank s are due to E imer Ame nd Ne w Y ork to the L eeds , ,

Nor t hru p C ompany P hil adelphia t o Dr A F H o ll em an

S
. . .
, ,

a n d to the publis hers for pe rm i ssio n to use certain cuts .

uggestio ns and criti ci sms will be appreciat e d .

h ost Ne w Y ORK
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M arch 1 9 2 2
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 C O N TE N TS

Lrsr

1
or R E FE RE NCE S

Determ i nati o n o f v ap o r ensi ty d

G w
.

A u sing Vic to r M ey er s apparatu s

,
’

B u sing We is er s m o difi e d V M apparatu s

,
’
. . .

2 . raham s effu si o n l a
’
Densi t y o f ga s e s
. .

3 Vapo r pre ss ure o f liq u ids

w
.

4 . S urfac e ten si o n and a sso c i at io n fac to r o f liqu ids

5 Refrac tive i n d ex d e n si t y a nd m o l ec ul ar refra c t ivi ty o f liq u ids

w
.
,

6 . Lo ering o f the free in g po in t z

A u si ng the B ec k mann metho d

w
,

B u si ng the De ar va c uum tub e meth o d and a no n el e c tro ly te ( urea)

,
-
.

C u sin g a Dewar v e ss el and an ac id

w
,
.

7 . M o l ecu l ar e ig ht d eterm in atio n u sing E y km an s b iling po i n t apparatu s

,
’
o .

8 . D is trib uti o n o f a s ubs tanc e b etween t wo no n mis c ibl e li qu ids -

9 . Dis t ill at io n i th s team

,

10 .

1 1 . B o ili ng p in t and vapo r c o mp o si t i o n c urve o f liqu id m ix ture s

o

So l ubili ty c urve fo r a ternary sys tem o f li qu ids

’

1 2 .

1 3 . Transi t io n po i n t s in the s li d s tate o .

1 44 P ha se di agram fo r a t wo —c mpo nen t sys tem o f metals

o

15 . M o no mo l e c u l ar rea c t i o n : i nversi o n o f c an e su gar

-
.

16 . B i mo lec ul ar reac tio n : sod ium thi o su l phate rea t ing w i th ethyl b ro m c

I7 .

18 .

1 9 .

20 . Adso rpt i o n o f disso lv e d s u bs tanc e s by c harc al o

21 .

23 . Hyd ro gen io n c o nc en trat i n e l ec tro metri c t i trat io n

o ,

24 . El ec tro mo t ive fo rc e mea s uremen t s c o nc entrat i o n c e lls ,

 OT T T T
LI S T O F R E F E R E N C E S

QU ED I N HE EX

w
A Textbooks
.

B I G E LOW Th eo ret ic al and P h ysic a l C h em is try The ,

C en tury Co Ne Yo r k .
,

O utli ne s o f The ret i c al C hemis try 3 rd E d o , .

,

W il ey So n s New Y r k ,
o

E l emen t s o f P h ysic al C hem is tr y 4t h E d , .

,

Mac m ill an Co N ew Y o r k

I
.
,

Te x tb o o k o f P h ysic al C hem is try rev E d , . .

,

Heath C N ew Y o r k o .
,

M L L ARD P h ysic a l C hem is tr y fo r C o ll ege s M c Graw ,

H ill B o k Co N ew Y o r k
o .
,

M OR GAN E leme n t s o f P h ysi c al C hem is try 4 t h E d ,

.
,

Wil e y So ns N ew Y o r k ( 9 08) ,
1

S E NTE R O ut li n e s o f P h ysic al C hem is try 4 t h E d , .

,

Van No s tran d Co N ew Y o r k

UN
,
.

W ALKE R I ntro d u c t i o n t o P h ysic a l C hem is try 9 t h E d ,

.
,

Mac m ill an Co N ew Y o rk .
,

WA SH B R P r i nc i pl e s o f P hysi c al C hem is try M c Graw ,

Hil l B o o k Co N ew Y o r k .
,

3
. Lab o r atory M anuals
B I LTZ (J o ne s Ki ng )
-
P rac t ic al Metho ds o f Determi ni ng M o l e c

I
u l ar We ig ht s C hem i c a l P ubli s hi ng Co
, .
,

Eas to n P a , .

B R GG S L ab o rat o ry O utli ne s in P h ysic a l C hem is try ,

Ithac a N Y ,
. .

P h ysi c a l C hem is try Th eo ry an d P rac t ic e

G
, ,

B l a kis to n P h il a d e lphi a
,

P rac t i al P h ysic al C hem is try grd Ed

c , ,

Lo ngm ans reen Co Lo nd o n

, .
,

P rac t i al P h ysi c a l C hem is try Van N

c os

w
,

trand Co N ew Y r k o

L ab o rato ry Ex erc is e s in P h ysic al C hem

ist ry 2nd E d W il ey 8: S o ns N e
, . Yo r k
, ,

1 9 08)
V111 OF R R E FE E NC E S

Mac m ill an Co Lo ndo n

R
.
,

La bo rat o ry Ex erc ises in P hysic al C hem

is t ry Univ ersi ty P ress Manc he s ter
, ,

OTH ( C amero n)
No s tra nd Co New Yo rk .
,

P hysic o C hemic al M etho ds B l akis to n P h il

-
,

ad elph ia

G
The P ri nc i pl es f A pp li ed El ec tro c hem is try

v
o ,

Lo ngm a n ree n a nd Co Lo nd n
s, .
, o

The rie f So l utio ns Ya l e Universi ty P ress

o s o , ,

New H a en

G w
B ANCR o rT A pp li ed C ll id C hemis try Mc Gra w Hill o o ,
-

B k Co New

G
oo .
,

D E NNI S as Ana lysis Macm illa n Cc Ne Y o rk , .

,

( 1 9 1 3)
FIND LAY The P hase Rul e 3 d E d Lo ngmans reen , , ,

a nd C Lo nd n o .
,
o

H ATSC H E K La bo rat ry M a nual f El eme ntary C ll id

o o o o

C hemis try B lakis t o n P h il ad e l ph i a

, ,

I I O LL E MAN ( Wa lk er) A Te x t bo o k o f O rg a nic Chem is try st h E d , ,

W il ey nd So ns New Yo rk
a ,

Le c ture Dem ns trat i ns in P h ysi al C hem o o c

is t ry T he C hemi c a l P u blis h ing Co E a s to n

,
.
, ,

Pa

L
.

LE Ac rI -
W rNr O N Fo o d I ns pec ti o n and A nalysis 4 t h E d , ,

W il ey nd S ns New Y rk

L
a o ,
o

E B LAN C ( W h i t ne y B ro wn ) A Te x t b o k f Elec troc hemis try M ac mill an

G
,
: o o ,

C o . New Y rk
,
o

E WI S A Sys tem o f P h ysic al C hemis try in 3 o l v

umes 3 d E d Lo ngman
,
reen and C ,
s, o .
,

Lo nd n

R
o

OS TW A LD-W O LS KI P ra k t ik um d er K ll idc hemi e 3 d E d o o , ,

S te i nk pf Le i p igo ,
z

O B IN S O N The El eme nt s o f F rac t i na l D is tillati n o o ,

M c G ra w H ill B k Co N ew Y o r k
-
oo .
,

t o n, Phil ad e lphi a
New Yo rk
New Y rk o
 LAB O RATO RY MA N U A L O F
P H Y S I CA L C H E M I S TRY

E XP E RI M E NT 1 A

D E TE R M I NATION O F VAP O R D E N I TY S
O b j e ct
Todetermine appro ximate molecular weights by the v apor
density method usi n g V ictor M eyer s apparatus
,
’
.

R e fe r e nc e s
Te xtb o o ks
B igelow X II V apor D ensities p 1 6 5
, , ,
.

Getman I I Gases p , , ,
.

SS S
Jo n es II Gases p 60
, , ,
.

L incol n I V D e t e rm n of M 01 S ym b W t s p 3 2
'

’
. . .
, , ,
.

M illard I I P rops of ubs in the Gaseous tate p 4 2

S
. .
, , .
,

M organ I I Th e Gaseous tate p 1 8

, , ,
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en ter I I Gases p 3 7
, , ,
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Walker XIX M ethods of M 01 Wt D e t e rm n p 1 9 4

, ,
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’
,
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B iltz ( Jo n es King) Gas Displacement M eth od , p 6

-
, .

B riggs II V apor De n sit y p 8

, , ,
.

E well I Gases p 9 3
, , ,
.

F i n dla y II I Den s of L i q uids

,
Gases p 49 ,
.
,
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F irth I I De n s of G ases L iquids V ap o rs p 8

, ,
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, ,
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Getman I I Vol ume De n sity p 3 0

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G ra y E x 3 Det of Vapor De n sity p 39

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.
,
.
,
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R oth ( C amero n) I I Determin ation of Densit y p 23 , , , .

2 LABORAT ORY MANUAL OF PHYS I CAL CHE MI STRY

H olleman ( Wa lk er) Te x tboo k of O rgani c C hem i stry

, ,

P ar II D e t e rm n of M 01 W t p 60
’
.
,
. .
,

v an Klooster L ecture Dem

, I V V P 81 Det of M 01 .
, , . . . .

Wt , p 35

Apparatus an d Ch e m i ca l s r e qu ire d
2 iron sta nds
2 clamps

I
2 iro n ri ngs
I wire ga uze

I
B un se n b u rn e r + ru b b e r tubing
I Victor M eyer outer jacket
Victor M eyer in ner tu b e suspe nded in glass jacket
I graduated (0 1 00 c c ) measuri ng tu b e ( nitrometer
.

tu b e with dou b le b ored stopcock )

plai n levelin g t u b e + ru b b e r tu b i ng
small glass co ntain er with capillary stem
co n triva n ce to close inner tu b e and to hold glass con
t a in e r ( s e e F ig 2 )
.

the rmometer (0
small E rlenmeyer flas k
te s t tu b e
S ample b ottles with aceton benz ene e t her etc , , ,
.

S a nd
P umice sto ne

Th e whole arra ngeme n t is readi ly u nderstood from F ig 1 . .

Th e inner V ictor M eyer tu b e ( a b out 8 mm in di am eter a nd .

a bout 7 5 cm lo ng) is e nl arged at the bottom s o as t o hold a b out

.

2 00 c c . Through a piece of gas tight ru bb er tu b i ng i t is con

-

n e c t e d with the measurin g tu b e Th e la tter is fur nished W i th a

.

two way stopcock al lowing co mmu nication with the atmosphere

-

jacket in whi ch the inner tube is suspe nded contains water and
D ETER MI NATI ON OF VAP O R
4 L B A ORATOR A AL Y M NU OF PH YSIC AL C HE M I S TR Y

a few pieces of pumice sto n e to insure regular b oiling In order .

t o pre vent the inner tube from strikin g t h e ja ck et a split cor k ,

is fastened just a bo ve the bul b of the fo rmer .

M e tho d of P ro c e d ur e

Dry the i nn er tu b e (which shoul d contain a little sa nd ) b y

inserting a lo ng glass tu b e ex tendi n g to the bottom
a n d b lowi n g or sucki n g air through .

S uspe nd the i nner tu b e in a centra l position

i nside the glass jacket a nd s e e that the b ottom is
wel l a b ove the surface of the water in the bul b .

Weigh a sma ll glass bul b with ca pillar y stem

(holdi n g a b out c c o f li q uid)
. drawn from a
piece o f glass tubi ng and then fil l it wi t h the
li q uid to b e evaporated .

To fi ll t h e b ul b po ur some of the li q uid into a

,

small test tube placed i n a small E rle nmeyer flask

( F ig and dip the stem o f the co n tai ner the
.
,

b ul b o f whi ch h as b ee n warmed in a flame in the ,

liq uid B y alternately coo ling a nd warmi n g the

.

b ul b enough li q uid is drawn in to cause a weight

,

P ro . 2 .

of
ic r e as e gr am B end the upper e nd of the stem o ver
.

a b ur ni n g match sea l the stem a nd again weigh the bulb

w
.

S uspe n d the contain er from the iron ire fastene d to the

device which serv es t o close t h e V ictor M eyer tube ( F ig .

to the o uter jack et .

 DE T R AT
E M IN I ON OF V P A OR T
D EN S I Y 5

When the a i r wi t hi n the i nner tube has reache d the tem

t u r e o f the steam jacke t an d is u n der atmospheric pressure
p e ra

( which is ascertai n e d b y co nn ecting the measuri n g tube al ter

matel y to air an d t o the i nn er tu b e a n d n o ting whether there i s
any cha nge o f l evel ) turn the stopcoc k so as t o connect the
measuri n g tu b e with the V ictor M e v e r tube a n d rea d the bo tt o m
o f the m eniscus .

B rea k t h e stem o f the c o n tainer by a sh o rt pull taking care

:
,

not t o rem ov e the st o pper from the inn er tu b e duri n g the opera
t ion .

Th e l iqu id s low ly v ap o r iz es e xpel l i n g the air i nto the m e asu r

,
.

ing tube Lower t h e l eveli n g tu b e t o k eep the system a ppro xi

.

mately under atmospheric pressure When m axim um displace .

ment of air has taken place bri n g the system e x act l y to atmos
p h e r ic pressure b y adjusting the leveli n g tube a n d turn the
J °
S topcock through 9 0 there b y shutting o ff the air in the measuri n g
tu b e from the v apor in the V ictor M eyer tube At the same time .

bre ak the rubber c o nnection be tween both tubes an d remove

the flame .

Rea d t h e v olum e o f the air in the measuring tu b e ascertain ,

the tempe rature of the water and the b ar o metric pressure

, .

O b s e rvati o n s an d M e a sur e m e nt s

Liqui d use d taken from bottle labeled

“

S
Weight of glass bul b .

We i ght o f bulb + liquid

ame after seali ng b ul b

S
Volume rea d ing at start
ame at end .
.

Vo lume o f a ir c o llected cc
. .
6 LABORATORY MANUAL OF P HYS I CAL CHEMI STRY

Vapo r pressure of water at this temperature

S ame corrected mm .

C orrected press ure o f di sp l aced air

F rom t h e weight of t h e li q uid the volume temperature and

, ,

pressure of the e xpelled air calculate :

1 . Th e specific gravity of the vapor with respect to air .

2 . Th e de n sity o f th e vapor u nder standard conditions .

3 . Th e molecular weight of t h e compound .

 E XP E RIM E NT 1 13

D E TE R M I NATI O N OF V AP OR D E NS I TY

( ALTE RN ATE M E TH OD)

.

Obj e c t
To determ ine vapo r densiti es using Weiser s modified Victor ’

M eyer apparatus ‘
.

Re f e r e nce s :

Jour . P hys . C hem .

,
20 ,

p .
53 2

Appar atu s an d Ch e mi cals r e quire d

2 iron stands
1 clamp
3 iro n rings
H

H B un sen b u rn e r + ru b b e r tub i ng
H outer jacket for Weiser apparatus
H Weiser apparatus with c o rk to fit ou ter jack et
H eudiometer tube ( 50 c c ) . .

H glass or po rcelai n di sh to serve a s pneumatic tr o ugh

H therm ometer (0
N
(
small glass stoppered bottles capacity ,
—
0 5 c c . . .

S ample bottles wi th benz ene chl oroform ether etc

, , ,
.

P umice st o n e
10 LAB ORATORY MANUAL OF PHYS I CAL CHEM I S T RY

jacket by mean s of a cork split verticall y wi t h holes to fit the

i nl et a nd e xi t tu b e of the apparatus a nd th e ben t glass tu b e
-

for the escape of the steam Th e two portions of the cor k are
.

fas te n ed firml y together b y means of a wire ar o und the top .

M e th od of P r o c e d ur e

F ill the b ulb of the jacket two thirds fu ll of water and sup
-

po rt the jacket o n a wire gauze in a q ui et place free from air

c urre n ts .

P lace the i nner tube in po siti on an d fasten it securel y b y

mea ns of the cork F ill the dish whi ch ser v es as pneumatic
.

trough with water and let the end of the Capillary de livery tu b e
dip b e neath the surface of the water F ill the graduated e ud io m
.

eter tu b e with water i n vert it a nd Clamp it n ear t h e delivery

, ,

tu b e in such a way t hat it ca n b e q uickl y moved over t h e tip .

H eat the jacket wi th a low flame and as soo n as the water

b egi ns to b oil adjust t h e height of the flame i n such a mann er
,

that steam just esca pes from the b e n t glass tube .

Weigh a b out gram of the assign ed liquid in t o t h e small

glass stoppered vial a nd stopper tightl y .

C lose t h e vaporiz atio n tu b e by a ru bber s t o ppe r a nd c o n

t in ue to bo il t h e water in the jacket Whe n no more a ir bub b les
.

are see n to escape from th e capillar y de li very tube remove ,

the stopper and place the eu d iometer o ver the tip of the d el i ver y
tu b e
.

Loo sen up t he stoppe r of the litt l e vi a l s o that it w ill not

stick later on dr op it into the vapo r iz ati on tube with the left
,

hand a nd immediatel y close th e tube with the stopper held

in the right hand bein g careful to s ecure an a ir ti ght joint
,
-
.

Th e s am p l e v apo riz es and dri ves ai r in t o t h e measur ing

tube .

When air bubbles no longer come o ver int o the eudiometer

tub e rem o ve the ru b ber stopper again turn off the gas an d
, ,

transfer t h e stand carrying the eudi ometer and pn eumatic

trough to a place where the temperature o f the gas col le cted ,
 D ETER MI NATI ON OF VAPOR D ENS I TY 11

R ecord the v olume of gas the height o f the meni scus o f the
,

w ater inside the eudiometer a b ove the level of the water in the
trough the temperature o f the surr o un di n g air and the bar o
,

metric pressure .

O b se rv atio ns an d M e as ur e m e nt s
L iqui d
use d taken from bo ttle labe l ed .

Weight of glass stoppered vial H iq uid -

.

Weight of vial empt y .

Wei ght o f li quid u sed

V o l ume of air c o llecte d

H eight o f water meniscus
R oom temperature

S
B ar o metric pressure
ame corrected
V apor pressure o f water at room temperature .
1

P ress ure o f a ir c oll ecte d .

F rom the weight of the liquid the v o lume the temperature

, ,

and the pressure of the air collected calculate

1 . Th e specific gra vity o f the v ap o r with respect to air .

2 . Th e density o f the v apor under standard cond itions .

3 . Th e m o lecular weight of the c o mp o un d .

1
Co nsu l t Tab l e 1 , App endix:
G RAHAM ’
S E FF U S ION L AW ; S
D E N I TI E S O F GAS E S

O b j e ct
’
To apply Graham s effusi o n la w t o the d eterm inat io n
gas de n sities .

R e f e r e nc e s
Text bo o ks

S S S
B igelow X I Gases p 1 4 2 , , ,
.

L in c o ln V I I I Kin Theor y o f Gases p 8 7

, ,
.
,
.

M illard I I P r o ps of u b s in Gase o us tate p

S
, ,
. .
,
.
48
M o rgan II Th e Gase o u s tate p 1 9
, , , .

en ter I I Gases p 3 3
, , ,
.

La bora to ry M a n u al s .

I Gases V ap o rs and L iqu id s p 9 4

E well , , , ,
.

Gray E x 2 D e t e rrn n o f D ens of CO2 p

,
.
,
’
.
,
.
38

Denn is Gas Analys i s , ,

p .
46

Apparatu s an d Ch e mi c al s r e quire d :
,

H tall glass c y li nder ab o ut 4 X 24 i nches ,

H e ffusi o n tu b e dimensi o ns I X 20 i n ches ,

H two —hole rubber stopper t o fit effusio n tube

glass stopcocks o ne straight o n e bent at r i ght
'

N , ,

H wood Clamp with tw o b o lts ,

H l ead disk for weighting tube ,

small platinum f o i l ( a 5 m g we ight)

S
H .

mal l bore rubber tub ing

.
14 LA ORATOR A AL
B Y M NU OF PH YSI C AL C HE M I S TR Y

Th e apparatus ( S ch illing s) is arranged as S hown in F ig 5

’
. .

Th e e ffusio n tu b e held tightly at it s upper end b y mean s of a

,

wood c lam p weighted by a lead disk is su b merged in the water

,

to a certain depth which must not change in order that the aver
age pressure under which the gases e fl u se remain the same
t hroughout t h e whole e xperim e n t Th e hole i n the plati num
.

fo il through which the gases e ffuse must

b e exceedin gly small I t is pun ched b y .

mea ns of a very fin e needle and if

n ecessar y c an be hamm ered down unt il

a very small ope ni ng remain s Th e .

foil is ceme nted t o the e nd of st o pcock A

b y mea n s of chi na cement or universal
wax ( a mix ture of o ne part of ve ne
tia n turpe ntin e and four parts of bees
wax) .

M e th od of P r oc e d ur e

stopcock A open B and fill the

Close
e ffusion tube with air ei t her b y b low ,

in g it in from t h e laborator y air li nes

or b y lift ing t h e tub e o ut of the water .

Close B replace the tu b e and se e

,

S
that the water in the outer cylinder rises
to within an inch of the top .

ee that the water in the apparatus

is saturated each time with the gas

FI G 5 .
u n der observatio n and that it h as the

S
tempe ratur e of the room .

With stopwatch in hand open stopcock A and all o w the ai r

,

to pass thr ough the ope n in g in the foil ta rt the watch when
.

the ris ing water passes t h e mark on the lower constri cti on of
th e e fl u sio n tu b e and stop it when the water passes the mark .

o n the up per constriction .

F il l the tube again with a ir an d repeat the o bserv ati o n and

whi ch check to tw o -
fift h s o f a sec o nd .
 G RAHAM S EFF US I ON LA W ; D ENS I TI ES OF
’
A
G SE S 15

O pen both st opcocks an d

pass h y drogen through the appa
ratus until all the air has been replaced by hydr o gen then close ,

A and fill the tube with h y dr o gen raising it if necessar y to secure

,

the entr y o f a su fficient am o unt of gas .

C lose B o pen A and recor d the t ime require d for this gas
,

t o e fl u se through the ope n in g R epeat the operati o n u n til

.

at l east three goo d checks hav e been o btained .

R ep l ace the residual h y dr og en with il lum i nat in g gas from

the laborator y fuel lines perf o rming the o perati o n u n der the
,

h o od to preve n t the escape of toxic gases into the ro o m .

O perate as before an d o b tai n at least three determinati o n s

which check t o two fi ft h s o f a sec o nd
-
.

Re co r d of O b servati on s
G as used
E ffusio n time

Ga s used
E ffusio n t ime

Gas used
Effusio n time

Gas sed u

E ffusion time

Cal c ul at i o n of Re sul t s
’
1 . B y means of Graham s effusion l a w ca l culate the
'
,

specific gravit y ( air = I ) o f each of the gases used .

2 . F rom the specific grav ities calculate the densit y of

,

each gas .

3 . C alculate the m ol ecular weight ( f o r ill um i nat i n g gas

"
t h e app aren t mol e cul ar w ei gh t ) .
18 LA ORATOR
B Y MANUAL OF PH YSIC AL C HEM I S TR Y

Apparatus an d Ch e mi cal s r e quire d

1 iron stand
3 Clamps

1 co nde n ser
I stirrer driven by a smal l motor
,

2 liter beak er
— 1
I

1 electric hot plate

1 thermometer (0
1 b arometer tu b e and 1 open mercur y manometer ,

attached to t h e same meter sti ck ( inn er diameter

of b oth tu b es 3 mm le ngth 90 cm ) .
,
.

1 4 gallo n bottle
-

1 water pump
1 is o t e n s is c o pe with tight fi t t ing ground glass joi n t
- -

1 two wa y stopcock a n d 1 ordin ary stopcock

-

S am ple bottles co n tai ni ng li q uids to b e tested .

To W a ter

FI G . 6 .

Th e arrangemen t is readil y understo od from Fig 6 Th e . .

iso t e ns isco pe co n sists of a c ylin drica l bulb of a b out 2 5 c c -

. .

capacity sealed to a 1 0 c c pipette bent as shown an d co nn ected

-
. .

to a reflux co nden ser by mean s of a grou n d glass joi n t Th e -

.
 VAPOR P R R L
E SS U E OF I Q UI D S 19

and o n the right through a two wa y stopcock A either with

,
-
,

the air or wi t h a large 4 gallon b o ttle which ser v es as a press ure

-

regulator B y means of a bent tube pro vided with a stopcock

.

B connecte d to a water pump the s y stem can be evacuate d

,
.

M e th o d o f P ro ce d ure

Assemble the apparatu s as sho wn in the fi gure c o nnect in g ,

the empt y iso t e nsisc Op e clean ed and d r y t o the condenser

S
, , ,

and appl y suctio n .

hut B se e that the pressure i s maintain e d and that no

,

leaks develop Th e pressure of the s y stem is represe n ted b y

.

the difference i n height of the mercur y in both tubes ( accurate

to 1 mm mercur y) Th e barometer readi n g i s compare d with
. .

that of the standar d lab o rat o r y bar o meter and a correctio n

applied if necessar y .

When found t o be i n w or king o r d er the pressure i s br o ught ,

back t o atmospheric b y carefull y and slowl y opening A to air .

D i sconnect the iso t ehsrs co pe an d fill the c y li n drical bul b

two thirds ful l of the l iquid u nder observation usi n g dimi nishe d
-
,

pressure to f o rce the liquid from the pip ette into the bulb .

M ake a tight joi n t with the co n denser .

F ill the beak er with water ( or glycerol f o r temperatures ,

abo v e in sert the thermometer placi n g the bulb n ex t t o

the middle o f the c o ntainer an d stir the l iquid v igoro u sly b y
,

mea n s of the motor driven st irrer -

.

When the temperature appro ximates the boiling poin t of

the liquid some o f it disti lls ov er and con den ses in the bent part
of the iso t e nsisc o pe 1
.

Th e heat is then tur n ed o ff an d the substance allowed to

c o ol Th e bubbles co n tinue to flow thr o ugh the l i q uid u n til
.

the liquid cools to t h e boili n g poin t temperature ( at atmos-

ph e ric pressure) when bubbling ceases and the liqui d is o n the

, ,

poin t of bein g sucked back i n to the small bulb on the right .

d
This prelim inary bo ili ng is c o n tinue d fo r so me t ime t o remo v e all the a i r
1

a nd i n s ure a un ifo rm temperature thr u g h o ut the li qu id

o Fo r m i x ture s t o wh i c h
.

the o peratio n c n a lso b e appli e d th e b o iling s ho u ld b e fo r a sho rt peri o o nly

a

a s p r l o ng e d b o ili ng wil l c ha ng e the c o mp o si t i o n c n sid era bly

o o .
20 LABORATORY MANU AL OF P HYS I CAL C H EM I STRY

As soo n the li q uid reaches the b ottom Of the small b ul b t h e

as

pressure a n d the temperature are read .

Th e two way stopcock A is t hen im mediately Opened t o the

-

pressure reservoir stopcock B is opened and suction applied

,
.

Th e mercury in the open ma n ometer is allowed to rise ab out

5 cm a n
. d the stopcock B closed T h e li q uid b oils agai n bu b bles
.
,

flow through the b e nd un til o n fur t her cool ing the flow Of b ub
b les stops and t h e li q uid again sucks b ack as b efore Temper .

atur e a nd pressure are the n read a nd noted This cycle of .

O peratio n s kn ow n as the method O f R ams ay a n d Y ou n g is

, ,

repeated u n til the li q uid h as cooled down s ufli c ie n t ly ( to a b out

°
20

F i nally the stopcock A is slowly ope ned to air a nd the system

aga in b rought u nder atmo s pheric pre s sure B is the n ope n ed
.

a n d the water p ump S hut o f f .

S top the motor disco nnect the is o t e ns is c o pe a nd remove

,

the li q uid from the in strume n t .

O b servation s an d M e a sure m e nts

L i q uid used
B arometer readi ng
S ame corrected

Temperature P ress ure S ame corrected

 VAPOR P R R
E SS U E OF L I Q UI D S

P lot the results on c oo r di nate the pressures as o rdi

nates against t h e temperatur es as abscissae on a suffi cientl y
,

large sca l e and c o nnect the p oi nts t h u s o bta ine d b y a sm oo th

cur v e
.
 I E NT 4
E XP E RII V

S URFACE TE N S I ON AND AS S OC I ATI ON FACTOR OF

L I Q UI D S

Obj e c t
To determi ne the surface te n sion and the m o lecular surrac e
e nergy O f a n assi gned li q uid and to calculate it s association
fa c t or.

Referenc e s

Te xt b o o ks

B igelow X III L i q ui ds p 1 80
, , ,
.

G e t man III L i q uids p , , ,

.

SS S
Jo nes III L i q uids p 1 45
, , ,
.

L i ncol n XI P hys P rops Of L iquid s p 1 1 5

, ,
. .
,
.

M illard I I I P rops of u b s in t h e L iq tate p 67

S
. . . .
, , ,

M orga n I II Th e L iqui d tate p 78

, , ,
.

S
S enter V Dil ute o lutio ns p 1 2 5
, , ,
.

Walker X I X M eth of M o "Wt D e t e rm n p 206

, ,
. . .
’
,
.

Washburn III Th e Liq tat e o f Aggrega t io n p 43

, , .
,
.

E well ,I Gas es V apo rs 81 L iqui d s p 1 77

, , ,
.

F indlay V Viscosit y 81 S urf Tens p 88

, ,
.
,
.

F ir th III D e t e rm n of Vis 81 Surf Te nS p ’

8
‘

, ,
. . .
,
. 1
 SU RA T O
F CE E NS I N AND A O AT O F
SS CI I N A CTOR 23

Apparat u s and Ch e m i c al s r e quire d

H i ron stan d
H ir o n ri n g
H clamp
H tall 2 liter beak er
-

H large test tube 3 5 cm lo n g di ameter 4 cm

.
, .

N capil l ary glass tubes wi th unif o rm b o re 3 5 ,

d iameter O bore ab o ut 0 3 0 5 mm
f —
. . .

H stirrer for beak er

N small scales graduate d i n mm .

H thermometer (0
H rub b er tub e 5 mm b o re 50 cm lo ng
,
.
, .

H B unsen b urn e r + rub b e r tub i ng

H wire gauze
H bottle c o ntai n in g d ry pur i fied mercur y

S
H b o ttle co n tain i n g c l ean in g solution
H bottle contain ing distilled water
ample bottles Co n tai n ing o ther liquids to be tested
Th e apparatus as used in this exper i ment is illustrated in
F ig 7
. .

Th e l iquid u n der Obser v ati o n is placed in the large test tube .

Th e latter is s upported verticall y in the b eaker which serves

as a water bath Th e capillary tubes passi n g through a three
.

holed c o r k are m o unted vertically with their lower e n ds immersed

in the liquid in the test tube Th e graduated scales are fasten ed
.

t o the lo wer end s o f the capi ll ar y t ubes b y means o f tinned wire .

M e th o d of P r o ce d ure

Mar k the capillar y tubes i n such a manner that the y can

be easil y iden tified during the experiment .

I n tr o duce a colum n of mercur y about 1 0 cm l o n g int o each .

o f the tu b es and measure the len gth accurately .

Weigh the mercur y and calculate the diameter o f the tubes .

C lean the bores of b oth tubes thoroughl y with hot clea ni n g

solution wash out with water and finally rinse with distilled
,

water All other apparatus comi ng In co n tact with the liqui d

.
24 LABORA TORY MANUAL OF P HYS I CAL CHEM I STRY

u nder o b servation S hould also b e clea ned a nd kept clean durin g

the e xperim e n t .

P lace the capillary tu b es a n d scales in a vertical position

an d fix t hem there b y
adjus tment of the cork
t h rough which they are su s
pe nded .

P lace suflic ie n t freshl y

distilled water ( or oth er
assigned li q ui d ) inside the
1

test tu b e to bri ng the leve l

o n the scales .

F ill the b eaker with tap

water a nd usin g the stirrer
, , ,

b ri ng the temperature to
suc h a value that the li q uid
inside the test tube i s at

B low gentl y in to the

ru bb er tu b e conn ected t o
t h e test tu b e in order to ,

force t h e li q uid up in to
the capillaries to a height
greater t ha n that of e q ui
"
lib rium ; this is to wet
the tubes and to insure
,

FI G 7. .
that the li q uid will rise to
e q uilibrium height Avoid .

small droplets Of liq uid in the upper po rtio ns Of the capillaries .

M easur e t h e height to which the li q uid rises three times ,

distur b in g the e q uili b rium b y gently blowing into the ru b b er

tube b efore each observatio n .

v
Water is t o b e preferred as t he li qu id u nd er o bser ati n fo r the rea so ns
‘

w
o ,

that i t has a hig her s urfac e tensio n th an o ther li quids a nd that i t is no t nec e ssary
,

t o dry the ca p ill ar i es af t er c l e aning

. If O bs er v ati o ns are t be ma d e n li qu ids
o o

o ther than ater i t is better t d ry the cap ill ari es by d raw ing a c urre n t f h t
, o o o

air fil te re d thr u g h c o tt n thr o ug h them th an t o emp l o y th e u s ua l proc e d ure

, o o , ,
 E XP E RIM E NT 5

R E F RACTIV E I ND E X D E N S I TY AND M OL E CULAR ,

RE F RA CTI V I TY OF L IQ U ID S

Obj ect
To determine the inde x of refractio n a nd the de n sity of
a give n li q uid at the same tem perature and to fin d it s
a nd molecular refracti v ity .

Te xtb o o ks
B igelow XI V I ndex of R efractio n p 1 90
, , ,
.

G etma n III L i q uids p

, , ,
.

Jo n es I II L i q uids p 1 1 5
, , ,
.

S
L i n col n XII R efraction of L ight p 1 2 2
, , ,
.

M illard XI P hys P rops 81 M O" S tructure p 3 1 6

, ,
. . .
,
.

M orga n II I Th e L i q uid tate p 7 7

, , ,
.

S e n ter III L i q uids p 63

, , ,
.

Walk er X V Re l n of P hy s P rops to Co m p n 81 Co n
, ,
’
. .
’

’
s t it n p 1 50 ,
.

Was h b ur n VIII Re l n P hys P rops 8 Chem Co n

, ,
’
. .
1
.

s t it n p 80
’
.
,

E well , V L ight p 2 1 6 , ,
.

F indl a y VI O ptical M easurements p 9 7

, , ,
.

F irth VI II R efrac ti v ity M easur eme n ts p

, , ,
.
46
 D ENS I TY AN D MOLECULAR REFRA CTI VI TY 29

S pe cial Te xts

Winton F ood analysis V I I F ats 81 O ils p 1 49

, , , ,
.

W o odma n F ood an alysis I Ge n M ethods p 7

, , ,
.
,
.

Apparatu s an d Ch e mical s r e quir e d

1 refractometer
°
1 thermostat pre fera b l y at 20 C
,
.

p yk n ometer an d pipette with capil l ar y stem ( F ig 8)

SS ii
1 .

1 bottle co n tai nin g distilled water

ample b ottles co n ta n n g differe n t o rgan ic li q uids
ilk paper to clean prisms of refractometer
,

F ig represe n ts the Abb e refractometer which is widely

.
9 ,

used in this cou n tr y an d is most satisfactory for gen eral la b o

r at o r practice as it is easy to ha n dle and is so c o n structed that
y ,

i t can be used with daylight and gives values correspo n di n g to

'

“
t he D lin e F or accurat e setti n g it is necessar y however to
.
, ,

use s o dium light ( see p It con sists of two prisms of

.

flint glass wi th a refractive i n dex of which c a n b e separated

s o as to allow the in troductio n of a few drops o f liquid Th e .

prisms c a n b e rotated b y mean s of a mova b le arm M which

carries the readin g glass R Th e position of the border li n e
.

o f total reflection is o b served through the fixed telescope T and

by tur nin g the mova b le arm it is made to coin cide wi th the
intersection of the cross hairs in the telescope Th e are A is .

graduated so as to read directly refractive i n dices (between

an d to t h e third decimal place Th e fourth decimal .

is estimated with an accurac y of 2 u n its by mea n s of the len s

R . Th e compe n sator C composed of two similar Am ici prisms ,

r o tated simultan eously in opposite directio n s b y the milled head

'

H i s used to produce a dispersio n (C F) e q ual b ut opposite

,
—

t o that of the li q uid and permits the bor der lin e to be chan ged
from a colored b a n d to a sharp colorless lin e B y takin g the .

readin g on the divi ded drum D a n d usi n g the tab le supplied with
’

the in st ru m e n t t h e dispersion may also b e found A heati n g

'

arra n geme n t fur ni shed b y the maker s or else a large thermo ,

30 LABORATORY MANUAL OF PHYS I CAL CHEM I STRY
'

stat perm its t h e c irc u la t io n of water at a given

temperature through the casi ng of the prisms .

P lace t h e instrume n t o n a table near the

window b ut not in direct sunlight and pr o
, ,

vide a large co n stan t temperature bath making,

conn ectio n s for the circulation o f the water

t hrough the casings in a S low b ut steady stream .

Turn the latch L release the lower prism

,

a nd swi n g it in to t h e position S hown in F ig 9

. .

I n order to test t h e correctness of the ad

justme nt Of the refractometer place a drop Of
,

dis tilled water o n the glass s urface close the

,

prisms and secure them b y mea n s of the latch L ,

rotate the prisms b y tur ni n g the movable

( als o 10 the mirror G

 D ENS I TY AN D MOLECULAR REFRACTI V I TY 31

Tu rn the screw head H a nd thereby adjust the compe n sator

so that the c o lored band due t o dispersion disappears a n d a
'

sharp boun dar y l ine is Obtain ed .

F i n all y rotate the arm M until the lin e coi n cides with the
i n tersection of the cr o ss hairs an d take the readi n g t o the f o urth
d e c irn a l place . Als o read the temperature .

R epeat the readin gs at least t hree tim es and take the mean ,

comparing the result wi t h the data g i ven f o r w ater on Table 3

of the Appe n dix .

O pe n the l atch dr o p the l o wer pr i sm c l ean the polished

, ,

glass surfaces with a little alcohol and silk paper ( d o n o t use

filter paper) and operate on the li q uid (s) assign ed for i nvesti
g a t io n i n e x actly the same ma n ner a s outli n ed above .

I n order to b e a b le to calculate the molecular refractivit y

it is necessary to determi n e the de n sity o f the li q uid at the tem
p e r a t u r e for which the readi n gs were take n A n y o f the well .

k n ow n t ypes o f pykn ometers ma y be used A special form .

of pykn ometer which t he auth o rs prefer i s represented in F ig .

I t has the advan tage that it is n o t fragile c an be Operated ,

e q uall y well at temperatures above an d b elow that of the room ,

is readil y clean ed an d c a n b e made in a v er y short time b y any

one Of moderate skill in glass b lowin g I n case the pyk n ometer
.

has b een calibrated at di fferent temperatures onl y o n e Ob se r ,

i
vatio n of the li q uid at the desired temperature a nd o n e weigh ,

ing is re q uired to fi n d the den sity for that temperature .

Th e de n sit y is then g v en b y the formula

WD ’
(W
’
— W)
W W
in whi ch W i s the w eight of li q uid at t W the weight of
’ °
,
° °
water at t an d D the den sity o f water at t ( see T ab le 4 of
,

the Appen dix) Th e small fraction to be sub tracted is a cor

.

rection for the b uoyan cy of the air .

Th e stem Of the pipette ( see F ig 8) i s Of such l e n gth a n d

.

width that it passes though the n arrow capillar y tu b e co nn ect

ing the upper an d lower reservoir of the pyk n om eter an d reaches
down to the b ottom of the lower b ul b .

B ingham v an Kloo s ter and Kle inspe h n J o ur P h ys C hem 24 p 6

1
, , . . .
, ,
.
32 LABORATORY MANUAL OF PHYS I CAL CHEM I STRY

To fill the pykn ometer conn ect the pipette to the suction
,

voir of the Clea n dry pykn ometer with the li q uid under investi
,
‘

g a t io n then
,
pass the capillary stem of the pipette t h ro u gh t h e
capillary co nn ecti o n of the pykn ometer a nd withdraw the air ,

from the bul b b y suctio n Add e nough li q uid to fil l the upper

,
.

reservoir to a height of a few mm place the in strumen t in the

.
,

thermostat an d after therm al e q uili b rium has b een reached ,

withdraw just enough li q uid b y mea n s of the pipette to bring

the level in the capill ary co nn e c tio n to the mar k Dry the .

pyk n ometer and weigh it 1

E mpty t h e pykn ometer b y lower
.

ing the stern Of the pipette to the b ottom a n d suck the li q uid
out usi n g a water pum p as b efore Wash with alcohol the n .
,

ether a nd fin ally suck a curre n t of dry air through the ins t ru

me n t .

F i n d the weight of the pyknometer fir st empt y and the n ,

fil led wi t h water of the same temperature ( or if the tim e is ,

lim ited take thes e v alues from a table compil ed fo r the

pykn ometer)
O b s e rvati o ns and M e a sur e m e nts
A
R efractive index

Average v alue
Value given

1
Fo r vo latil e
 E XP E RIM E NT 6A

L O WE R IN G OF TH E FR E E Z I N G P O I NT

( B E C KMAN N M E TH OD )
O b j ec t
A To. determine the appro ximate molecular wei g ht of a
n o n dissociatin g compo und in solution
-
.

B TO dete rmine t h e appare n t molecular we i ght of an electro

.

lyte in solution a nd to calculate the degree of diss o ciation Of

the electrolyte at the concentrations employed .

Te xtb o o ks
B igelow XXI I I V ap P ress Of So l ns p 3 24
, ,
. .
’

,
.

G etm an VI II Dil S o ln s 81 C sm P ress p

, ,
.
’
. .
,
.

Jo n e s V S olutio ns p 2 2 8
, , ,
.

’
L in coln XXV Fr P ts 81 B oi 1 P t s of So ln s p
, ,
.
~
. .
-
.
,
. 2 78

M organ VI S olutio ns p 1 7 2
, , ,
.

S enter V Dilute S olutio n s p 1 20

, , ,
.

Walker XIX D e t e rm n of M O"W t s p 204

, ,
’
. .
,
.

La bor ato r y M a n ual s :

B iltz (J o n es King) Det of M 01 Wt b y F r P t M eth
-
,
. . . .
-
. .
,

p 73 .

S
B riggs V I Depression of Fr P t p 2 1
, ,
.
-
.
,
.

E well I Gases Vapors 81 L iq uids p 3 5

, , , ,
.

F in dl a y VI I M o l Wt Of ubs in So ln p 1 2 5
, ,
. . . .
,
.

F ir t h V D e t e rm n of M 01 W t s p 3 1
, ,
’
. .
,
.

G etm an VI M elting 81 B oil ing P oin ts p 70

, , ,
.

G ra y E x 1 1 Lo weri ng of F r P t p 5 7
,
.
,
.
-
.
,
.

P ring P art I P hys C hem M eas p 4

, ,
. . .
,
.
 LO R WE ING OF T H E F R EEZ I N G P O INT 37

Apparatu s an d Ch e mi c al s r e quir e d
1 b atter y jar for freezin g mixture
meta l co ver for same
1 metal pan
1 glass air jack et
1 B ec kmann freezin g poin t tube
1 B eckmann therm o meter
1 thermometer ( from — 1 0 to
2 stirrers o n e small o n e large
, ,

1 readin g glass
1 1 0 c c pipette
-
. .

1 two hole cor k carrying the B eckmann therm o meter

-

a n d small stirrer for freezin g poi n t tube

1 large c o rk for adaptin g freezin g p o in t tube to air

jacket
Ice a nd salt f o r freezin g mix ture an d samp l e tubes
with solute ( sugar urea a nd salts) , ,

Th e apparatus is S h o wn in F ig 1 0 A mix ture Of water . .

,

crushed ice and salt s ufficien t to reach within an i n ch o f the

,

top is placed in the large glass jar Th e air jacket is fix ed in

,
.

this freezin g mi xture through the cen tral aperture Of the co v er ,

a n d ser v es t o pr ev e n t direct co n tact between the B eckmann

freezin g point tube a n d t h e coolin g bath .

M e th o d o f P ro c e d ur e
P repare a freezi n g mix ture a nd mai n tai n its temperature
arou n d
B y mean s of a 1 0—C c pipette introduce s ufficien t distilled
. .

water in t o the freezin g tube to immerse t h e bulb of t h e B eck

mann thermometer M ake each additio n ex act ly 1 0 c c Th e
. . .

mass o f water used is determined b y n oti n g the temperature

a n d Ob ta ini n g the weight from T a b le 4 Appe n dix Pl ace the ,
.

thermometer and stirrer in position in such a mann er that the

stirrer moves freel y a n d immerse the tube directl y in the fre e z
,

in g mix ture .I t will be noticed that the water supercools several

de grees before freezin g be gins and that as soon as ice forms the
,
38 LABORA T ORY MANUAL OF PHYS I CAL CHEM I S TRY

temperature rises rapidly approa c hin g the freezi ng poin t ( heat

,

b ei n g li b erated b y the separatio n of ice) .

Take the freezin g poi n t tu b e from t h e cold b ath wipe it ,

dry and place it in the b ath all owin g e q uili b rium to be

,

atta ined S tir gently tappin g

.
,

the stem Of t h e th ermometer

at regular in tervals a nd record
read in gs every 3 0 seco nds esti ,

mat in g thousan dths Of a degree

b y mean s of a read ing glass .

Th e val ue o b tai n ed whe n read

i n gs have b e c ome co nsta n t is
take n as t h e freezin g po in t of
pure water P lot t hese results
.

o n coo rdin ate paper M elt the

.

ice a nd repeat th e determin a

tio n S ucces sive Ob servatio n s
.

S hould agree to wi t hin

b efore proceedin g .

I n tr od u c e a b out half a gram

of solute accuratel y weighed
, ,

a nd determin e the freez in g poin t

of the solutio n I nasmuch as .

the separatio n of the solid phase

( ic e ) co nce n trates the solution ,

it is necessary to ex ercise e x
treme care in havin g the smallest
po ssi b le amoun t of ice prese n t

I
F G 10 . .
at the time of fin al temperature
readi ng .I n case this pre c au

ti on is n o t Ob served res u lts wil l,

b e vi tiated When operating o n s o lutio ns it is best not to immerse

.
,

the freezin g poin t tu b e directly in the cold freezing mix ture S hould
- .

it however be n ecessary to do th is in order to initiate the cr y stal

liz a t io n it is advisa b le to melt the greater po rtio n of the ice b y
holding the tube in th e han d b efore placin g it in the air bath AS .
 L OW ER I N G OF THE FREEZ I N G PO I NT 39

temper ature has been located an d plot these values taki ng the
, ,

maximum temperature on the temperature —time curve .

Ad d t wo successive additi o n al weighed portio n s of about 0 2 gm . .

of s o lute and determi n e the freezi n g poi n t of each solutio n

, .

O b s e rv ati on s an d M e a s ur e m e nt s
Volume of distilled water used cc . .

Temperature
Density ( from Table 4)
Weight of water used

S S
Therm o meter readi ngs at half mi n ute i n tervals
-

Water olutio n 1 olutio n 2 S olutio n 3

L oweri n g o ffre e z
40 LABORATORY MANUAL OF PHY S I C AL T
C H E M I S RY

A . S olute is a no n electrolyte
-

1 Calculate the molecular weight Of the solute fo r

.

co nc e n tratio n used . co n

S
stan t from Table 5 Appendix
,
.

B . olute is an electrolyte
1 Calculate t h e appare n t molecular weight of the
.

for ea c h co nce ntratio n used

.

2 C ompute the degree of dissociatio n for each appare n t

.

molecular weight.

3 P lot appare n t molecular weight and degree of dis

.
,

sociatio n again st co ncentration e xpressed in

, ,

grams O f solute pe r 1 00 grams Of solvent .

 E XP E RIM E NT 6B

LO WE R I N G OF TH E FR E E ZI N G P O I NT B Y A NON
E L E C T R O L Y TE

( DE WA R VA CU U M TU B E M ETH OD)
O b j e ct
T0 determi n e the molecular weight Of u rea by the freezing
poi n t method usi ng a vacuum jacketed D ewar tube
,
-
.

J o urn al Articl es
R olo ff ,
f ph y s C hemie 1 8 p 5 7 2 ( 1 89 5)
Z e it s . . .
, ,
.

P o nso t An n chim phys ( 7) 1 0 p 7 9 ( 1 89 7 )

,
. . .
,
.

R ichar d s Jour Am chem s o c 2 5 p 2 9 ( 1 9 03 )

,
. . . .
,
.

Appar atu s and Ch e mi c al s r e quir e d

1 v acuum cylinder ( sui table d imensions 6 cm X 20 cm . .
,

c o n tents 500 c c o r 7 cm X 3 0 cm co n te n ts
. . . .
,

1 000 c c ) or a 1 qt wi de mouth Thermos flask

. . .
-
.

1 c o r k f o r m o uth o f Same carr yi n g

1 B eckmann therm o meter

1 glass tube with lin en filter a t l ower end

1 S hort glass tube

1 glass stir rer

readin g glass
cork to protect tip Of Dewar tube
corrugated cardboard packing filler

ir o n rings
44 LABORATORY MANUAL OF P H YS I CAL CHEM I STRY

5
-
c c pipette
. .

2 50 c c wide mou t h E rlenme y er flasks

- . .
-

1 5 c c weighi n g b ottles short form

-
.
,

o n e hole ru bb er stopper for E r le mn e y e r fitted with

-
,

piece Of glass tu b in g and short ru bb er connecti o n

graduated ( 0 — 1 00 c c ) gas measurin g tube . .

leveli ng tu b e + ru bb er tu b in g
the rmometer (0
small b ottle co n tainin g a b out 20 c c freshly made . .

saturated urea solutio n

1 5 00 c c b ottle co n tai
. n i
. n g a solutio n of sodium h y po
b romite freshly prepared b y di ssolvi ng 1 00 grams
O f caustic sod a in 2 50 c c of water and adding . .

little b y little 2 5 c c Of bromin e . .

1 ice S haver or c hipper

Ice

Th e assem b led apparatus is S h o wn in F ig 1 1 Th e vacuum . .

flas k with its tip protected b y a cork is wrapped in packin g

, ,

card b oard to preve n t in j ury and held securely o n a n iro n stand

b y mea ns O f two iro n r ings Th e cork fitti n g i n to the mouth.

of the flask is pierced b y four holes : the ce n tral one carrying

the B eckm ann thermometer and the three others the stirrer ,

a s hort glass tu b e through which urea is introduced and a lo nger

tu b e through which sam ples are withdrawn This latter tu b e .

should b e of such le ngth that t h e pipette used fo r withdrawi ng

solutio n s reaches just to the linen fil t e r 1
.

M e th o d o f P r o ce d ur e

F il l the Dewar vessel about two thirds full o f S haved or -

S
finel y crushed ice and add s uffi cient dis tilled water to permit
the stirrer to move freel y .

ee t hat the B eckm ann thermometer is se t so that the

mercury comes to rest n ear the top Of the scale whe n the b ul b
is imm ersed in ice water P lace the thermometer in position
-
.

with it s bul b near the center o f the m ixture of ice and water .
LOW ERI N G OF TH E FREE Z I N G PO I NT 45
 S
46 LABORATORY MANUAL OF PHYS I C AL C HEM I STRY

t ir regularly b ut n o t viole n tly a nd take temperature read

i ngs at half mi nute in tervals un til five successive constant values
-

have b ee n Ob tained This co n sta n t value is take n as the freezing

.

poin t of pure water .

B y mea ns of a 5 c c pipette i n troduce an amoun t o f urea

-
. .

solutio n su ffi cie n t to lower the freezi ng point ab out two tenths -

O f a degree Determi n e the freezing po in t of t his solut io n b y

.

the method outlined a b ove .

Without dela y pipette o ff through th e long glas s tube 1 0 c c

, . .

of solutio n a nd reject this ; the n take two 1 0—c c samples for . .

a n alysis a nd run these in to the 1 5 c c weighi ng b o ttles placed -

. .
,

inside the 2 50 c c E rle nm eyer flasks

. . .

B y mea n s of a 50 c c pipette put a b out 50 c c o f the h ypo

. . . .

b romite solutio n in each flask be ing careful t hat the tw o solu ,

tio ns do no t m ix
I nsert t h e perforated ru bb er stopper place o ne E r l enm eyer ,

flask in a clam p a nd connect it with the gas measur ing tube

,

( nitrometer ) .

R aise the water in t h e nitrometer to a po int near the top ,

secure atmospheric pressure within t h e system and tak e t h e

initial volum e readin g .

B y a ge n tle s win gi n g upset the small weighi ng bottle and ,

allow the two solutions within t h e E rlenmeyer flask t o m ix

thoroughl y As fas t as gas is evolved lower the leveli n g tu b e
.
,

in order to keep the system u nder appro ximate atm o spheric

pressure .

Whe n the gas evolution is complete all ow the reaction ,

vessel to come to roo m tempe rature b rin g the s ystem t o atm o s ,

p h e ric pressure a n d record the fin al volume .

Al so record the b arometric pressure and the r oo m temper

atur e .

In exactl y the same manner d eterm in e the vol um e o f g as

for the sample in t h e other flask .

F o llowin g the method outlined above 1 c c of gas ( nitrogen) ,

. .

u nd er s ta nd a rd cond i t io ns is e q uivale n t to gram Of urea .

Add two ad di tional volumes of urea solution to the vacuum

flask so that a furth er lowering of a b out
,
and is pro
 LOW ER I N G OF TH E F R EE Z I N G POI NT 47

d uc e d an d in
each case determine as b efore the freezing poin t
and t h e conce n tration of urea .

It is advisabl e that o n e student carr y out the freezi n g poin t -

determin ations an d his partner the gas evolution measurements .

Temperature rea d i n gs at half minute i n tervals

-

I ce water S olution
-
1 S olutio n 2 S o lutio n 3

Nitrometer readi n gs b efore a nd after gas ev o lution

S ample 1

S ample 2
 1 R educe the three ( average) gas volumes to standard
.

co nditio ns a nd calculate the weight of urea prese n t in each

sample I n asmuch as the solutio n s are ver y dilute these weights
.

may be taken as b ein g prese n t in 1 0 grams of water .

2 C alcu late the molecular weight of urea for each se t of

.

Observatio n s .

3 P
. lot molecu l ar weight aga in st conce n tration a nd connect

the po in ts b y a straight li ne P roject this line to the Y a xis ;

.
-

the po i n t of i n tersection represe nti ng the value for i nfinite dilu

tio n is the nearest approach to the theoretical molecular weight .
 E XP E RI M E NT 6 C

L O WE R I N G OF TH E F R EE Z I N G P OI NT B Y
AN E L E C T R O L Y TE

( DE WA R VA CU U M TU B E M ETH OD)
Ob j e ct
T0 determi n e the appare n t molecular weight of an aci d
in a q ue o us s o lution and to calculate the degree o f di ss o ci atio n
,

of this electr o lyte at the concentrations emplo y ed .

Apparatu s an d Ch e m i c al s r e quir e d
1 wide mouth v acuum flas k with access o ries as d e
-

scribed in E xperiment 6B I n stead of the nit ro m

.

eter outfit therein menti o n ed su b stitute : ,

1 iro n stan d ‘

1 b u re t t e h o ld e r
1 burette
1 10 pipette
1 2 c c pipette
-
. .

2 wide mouth 1 2 5 c c E r l enme y er flas k s

-
. .

1 small bott l e with di l ute ( 1 3 ) H C1 o r o ther aci d

1 stock bottle with tenth n ormal alkali
1 pheno lphthalein indicat o r s o luti o n

F or a sketch of the apparatus see F ig . 1 1 .

F ill the D ewar v essel wi th i ce an d water as d escri be d o n

page 44 an d determ ine the freezing point of water in the manner
52 LABORATORY MANUAL OF P HYS I CAL CHEM I STRY

By mean s of a 2 c c pipette in tro d uce a su ffi cie n t amoun t

-
. .

Of the acid t hr o u g h the short glass tu b e to lower t h e freezi n g ,

po in t a b out o ne tenth of a degree S tir regularl y and take

-
.

half m inute readin gs u n til five successive c o nstant readin gs are

-

O b tain e d .

H avi n g determin ed the freez ing poin t of this solution ,

immediately remove 1 0 c c of the s o lutio n through the fil ter

. .

tu b e reject t his a nd the n place two 1 0 c c samples for titra

, ,
-
. .

tion in t h e small E rle nm eyer flasks la b eled 1 and 2 ,

.

Titrate t hese solutions wi th sta n dard alkali us ing phenol ,

ph t halein as in dicator .

Ad d three additional successive amounts of acid to t h e

vacuum flask each giving a further loweri n g O f a b out o ne ten t h
,
-

of a degree and determin e the freezi ng po in t a nd the strength

,

of the solutio n in each case .

It is ad v isa b le that o ne stude n t carry out the freezin g poin t -

determi nati o ns and his part n er th e ti t ration s

,
.

Ob se rv ati o ns and M e asur e me nt s

Acidused in the e xperiment

Normality of a lka li use d for t i tratio n

S S S
Temperature readi ngs at half mi nute intervals

I ce water
-
olutio n 1 olution 2 S olutio n 3 o lutio n 4
 LOW ERI N G OF TH E FREEZ I N G P O INT 53

Number o f c c o f base used in titrating the so lutions

S
. .

ample 2

Average

No rmalit y o f
solution
Grams of acid
i n 1 00 grams
Of H 2()

1 . Assumi n g , f o r the d ilute solutions used that the weight ,

O f acid fou n d in 1 0 c c of solution s may be taken as presen t

. .

in 1 0 grams of water , substitute the weights o f s o lute present

"

in 1 00grams Of wate r in the ta b le abo v e

\
.

)
2 . B y mean s of th e freezi n g point equat io n ca l cu l ate the
-

appare n t molecular weight for each c o ncentratio n .

3 F r o m the apparent mo l ecu l ar w e ig hts ca l cu l ate the

.

degree Of d i ss o ciati o n .

4 P lot the v alues found for the dissociati o n aga i nst th e con
.

c e n t ra t io n s as abscissae .
 E XP E RIM E NT 7

M O L E CUL AR W E I G H T D E TE R M I NATI O N

( B O I LI N G -
P O I NT M E TH OD)
O b j e ct
TO determin e appro ximate molecular weights by the boili ng
poin t method us in g E y km a n s apparatus
,
’
.

Te xtb o o ks
B igelow X X III Vap P ress O f S olu s p 3 1 9
, ,
.
‘

.
’

,
.

G etma n VII I Dil So ln s 81 Osm P ress p

, ,
.
’
. .
,
.

Jo nes V S olutio n s p 2 6 2
, , ,
.

L inc o ln X X V Fr P t s 81 B Oil P t s of S o ln s
, ,
.
-
. .
-
.
’

M illard V S olutio ns p 1 2 5
, , ,
.

M orga n VI S olutio ns p 1 6 7
, , ,
.

S e n ter V Dilute S olutio ns p 1 1 4

, , ,
.

Wa lker X IX D e t e rm n of M O"W t s p 1 9 8
, ,
’
. .
,
.

B il tz (Jo nes Kin g) D e t e rm n of M o l W t s b y B oil P t

-
,
’
. . .
-
.

M e t hod s p 1 4 1 ,
.

B riggs V E levation of the B oil P t p 1 7

, ,
.
-
.
,
.

E well I II S olutions p 1 7 5
, , ,
.

F i ndl a y VII M o l Wt of S u b s in S olution p 1 4 7

, ,
. . .
,
.

F irth V D e t e rm n Of M OI W t s p 24
, ,
’
. .
,
.

Getman VI M el ting 8 B oiling P oi n ts p 77

, ,
1
,
.

Gray E x 8 R aising Of B oilin g P o in ts p 4 9

,
.
, ,
.

P ri n g P art I
,
P hys C hem M easurements p 9. . .
,
.

R oth ( C amero n) I II D e t e rm n o fM o l W t s in S o ln s p 4 7
’
,
’
. .
,
.
58 LABORATORY M ANUAL OF P HYS I CAL C HE MI STRY

S
M e th o d of P r oc e d ur e

in ce b oth the b oi ling poin t and t he volume of the solution

are read o n the therm ometer it is necessar y first to calibrate
,

the i nn er tu b e volumetrically .

I n doi ng this raise the i nn er vessel until its top comes flush
,

with the top of the outer jacket and

make sure that the i nn er vessel and the
therm ometer are both e xactl y vertical .

Th e latter should always rest o n the

b ottom of the inn er tube ;
F rom a b urette fil led t o the zero
mark with pure car b on tetrachl o ride ,

r un a who le num b er of c c into the . .

i nner tube un t il t h e li quid rises on the

the rmometer scale .

R ead the upper meniscus on the

scale .

Ad d e xact l y 1 c c at a time reading . .

,

the volum e each t im e o n the thermometer

u n til 2 5 c c have b een added
. . .

P repare a table which will sh o w t h e

volume of th e soluti o n in the tube at
a n y height shown on the therm o meter .

R em o ve enough o f the solven t from

the in ner tu b e to bring the lev e l t o the

FI G 12
. .
b ottom of t h e scale and place a b out 50
c c .of .pure
outer jacket
car b on te t rachl oride in the
.

L ower the E y km an vesse l so that the bott om of the inner

tu b e is just a b out 1 cm above the l e ve l of the liquid inside
.

the s u rro undin g c y lin d rical tube .

P lace a sm a ll flame under the o uter jack et and adjust the

flame in such a m ann er th at t h e vapo r c o ndenses ab o ut 5 cm .

a b ove the t o p o f t h e Eykm an tube ( at E F ig ,

.

the same When the thermomete r giv es a v alue c o nstant t o

.

hund redths o f a d e gree equilibrium h as been reached

, .
 M OL EC ULA R W E I HT D ETERM I NATI ON G 59

R a i se the i nner v essel till its top comes flush with the top
of the jacket and add from to gram of azo b enze n e ,

accuratel y weighed obser vin g care lest some o f it stick to the

,

thermometer o r the side o f the tube .

L ower the vessel to the s ame le v e l as bef o re and deter ,

mi n e the boi ling point of the s o lution B e sure that the solu .

tio n actuall y boils ; this c an readil y be seen b y ob servi n g whether

“

'

the v ap o r o f the solvent bub b les through the solution If this .

does n o t take place the in n er vessel should be lo wered a little

more .

R aise the tube t o i ts previous height o bserv e the volu me ,

using precaution to make sure that conditio n s are the same

as in cali b rati n g R ecord volume
. .

Add successively 3 weighed q uan tities o f azo b enz ene

gram ) a nd n ote carefu l l y the b oili n g poi n t and the volume
each time as directed above
,
.

When all the readings have been taken turn Off the gas , ,

rem ov e the thermometer pour the residue fr o m the v essel i n to

,

a b o ttle p rovi ded for this purpose an d ri n se both the thermome ter
a n d the tube with a few c c Of pure carbon tetrachloride tra n s
. .
,

ferrin g the liquid each time to the residue b ottle .

D O not attempt to ri n se a n d clea n the apparatus with water .

O b se rv ati o ns an d M e a s ur e m e nt s

Vo lumb readin gs on thermometer

scale readi n g
60 LABORA T ORY MANUAL OF PHYS I CAL CHEM I STRY

B oili ng poi n t of pure

every 1 5 seco nds :

0 0 0 0 0 0

Volum e readin gs in cc
. .

i
Cal culations

of the solut o n s 1 5
pure solve n t fin d the weight
,
 G
M OLECULAR W E I HT D ETERM I NATI ON 61

2 . E x press the four conce n tratio n s in terms of grams Of

s o lute in 1 00 grams of solven t "weight of sol v ent (S ) weigh t
Of solute (g) = r o o x"

3 R ecord the data Ob tai n ed

. A ( rise of b oiling poi n t ) ,

S g an d co n ce n tratio n in followi n g table

, ,

Co ll C

4 Appl y the boiling poi n t formula and calculate for each

-

c o n ce n trati o n the molecular weight of azobenz ene O b tain .

boilin g point co n stan t from Table 6 Appe n dix

-
,
.

P lot the molecular weights Ob tained as a fu n ctio n Of the

5 .

co n cen tratio n s a n d connect the poi n ts ob tained by a straight

l ine Where it intersects the Y —axis the value for the m o le c
.
,

ular weight at infi n ite d ilutio n which is the n earest approach

to the theoretical value is o b tai ned ,
.
 E XP E RIM E NT 8

D I S TR I B U TI O N O F SUB S TAN CE B ETWE E N A TWO

NON M I S C I BL E L IQ U ID S
-

Obj e c t

To deter m i ne the partitio n O f b e nzoic acid b etwee n water

a n d b e nze n e a n d to tes t the validity of Nernst s distri b ution
’

law in th is case .

Te xt b o o ks

B igelow XX IV P rocess of Ppt n 8 ol n p 3 50

,

G etma n XI I I H omogeneous E quili b rium p

, ,
,
’
1
S ’
,

,
.

L in co ln XV S o ln s of L i q uids in L i q uids I p 1 6 5
, ,
’
, , .

M illard v S olutio n s p 1 1 7
, , ,
.

M organ VI S olutio ns p 20 1, , ,
.

S e n ter VIII H eteroge neous E quilibrium p 1 7 7

, , ,
.

Wa lker XX M o l C omplexity p 2 1 6
, ,
.
,
.

Wash b urn X IV Distri b utio n L aws p 1 48 , , ,

.

E well , VI I Chemical tatics p 2 6 2

F in dlay VIII Dist of S u b s b etween 2
,
,

,
.
S ,

.
.

S olve n ts p 1 55 ,
.

F irth XI D e t e rm n of P art Co e ff s p 7 1
, ,
’
. .
,
.

G ray E x 1 3 Distributi o n F acto r p 63

,
.
, ,
.
_

3 1 50- c c separato ry f unne l s labele d

. .
,
1 ,
2 and 3 with

1 5
- c c pipette
. .

1
those in the other two funn els in like mann er .

C areful ly draw a b out 1 7 c c of the lower ( a q ueous) l ayer

. .

from funnel NO 1 runn ing it i n to the d ry graduated cylinder

.
, .

R in se the 5 c c pipette with thi s solutio n then run exactl y

-
. .
,

5 c c i n to each of the E rle nme y er flasks add 2 0 c c of C02

. .
,
. .

free water a n d a drop of phe n olphthalein to each heat to boil ,

ing a nd titrate with b aryta solutio n .

After havi n g Ob tai n ed satisfactor y checks ( to

dry the measur ing cylin der a nd pr o ceed to the analysis of the
a q ueou s layer in the other two funn els .

B efore lea v in g the la b oratory se e that the soluti o n s are

,

drai n ed from the separatory f unn els R emove the stopcocks .

,

a nd leave the fu nn els supported in their ri ngs so that the y will

drain a nd d ry b efore the ne x t la b oratory period .

Ob se rva tions an d M e as ur e m e nts

No . 2

G rams of b e nzoic acid

c c Of water
. .

c c of b e nze ne
. .

Anal ysis e r ( be nze ne ) l ayer

o
f pp u

cc
. . Of b aryta

M ean of consta n t values

Ana lysis f lo wer (aqueo us )

o layer :
c c of bary ta
. .

0 0 0 0 0 0 0 0 0 0 0 0

o o o o o o o o o o o o o o o o o o

o o o o o o o o o o o o o o o o o o

M ean of cons tant v al ues

 D I S TR I B UTI ON O F SU S B TA NCE 67

1 . E xpress the numeri ca l the rat oi T

J
B
for the three

se e w hether a c o ns tan t v alue i s o b ta ine d o r not .

I f n o t , what c o nc l us i on can be drawn "

2 . C alcu l ate the rati o s an d I f either o f these

i s c o nstant what i nference can be draw n "

 S S
E XP E RIM E NT 9

DI TIL LATIO N W I TH TE AM

O b j e ct
To illustrate the prin ciple of steam distillati o n an d to S h o w ,

that the molecular weight of the less volatile con stitue n t can
b e determi n ed fr o m the partial pressures of the distilli n g vapors
a n d the weights of the li q uids Obtai n ed in the distillate .

Re f e r e n c e s
Te xtb oo ks

B igelow XX I V P rocess of o l ution 81 P pt n p 3 33

, ,
S ’
,
.

S
Getman VI I S oluti o n s p
, , ,
.

’
L incol n X V I S o ln s of L i q uids in L i q uids II p 1 8 1
, , , ,
.

M illard V olutio n s p 1 3 3
, , ,
.

S
S en ter I V So lutio n s p 9 0
, , ,
.

Wa lk er V II I V apo riz n 81 Co n den satio n p 80

, ,
’
,
.

Washburn X V I o lutio n s IV p 1 8 1
. . .
,
.

H olleman ( Walker) O rganic C hem i str y P ar

Distillation p 2 6 ,
.
, . . 23 , S team

R obin so n Th e E leme n ts of F ractio n al Distil l ation

, .

T a b le 3 Appe n dix pp 1 80 — 1 9 5
, ,
.

Apparat u s an d Ch e mi c a l s r e quir e d
2 iron sta n ds
2

1
70 LABO RATORY MANUAL OF P HYS I C AL CHEM I S T RY

co nn ectin g side arm still head

-

t hermometer ( 50 graduated in tenths of a

degree
3 0 inch c o n d e n s e r + rub b e r tubing
-

B un se n b u rne rs + ru b b e r tub in g
1 00 c c graduates
- . .

adapter
separator y fu nnel
2 50 c c E rle mn e y e r flask
-
. .

00 -c c bottle co ntai n i ng either

5 . .

(B P . . b romo b e nze n e P or nitro .

b e nz e ne ( B P . .

F ig 1 3 represe n ts the apparatus used for steam d istill ati on

. .

A roun d b ottom flask inclin ed at an a n gle is supp o rted on an

-

iron ring and closed by a two hole c o rk Thr o ugh o ne h o le

-
.

passes a glass tub e bent do wnward so as to reach wi th in

cm of the bo tt om of the flask whil e the o ther h ol e be ars the
.
,

s til l head which conn e cts the flas k to t h e c o nd e nse r A th er

'

m o m e t e r reading to ten t hs o f a degree is i nserted in the still

 DI STI LLATI ON WI TH S TE AM 71

c an is pr ovid ed wi t h a safet y tube whi ch reaches to the b o ttom

a nd ex tend s ab o ut 40 cm ab ov e the top . .

M e th o d of P r o c e d ur e

H al f fill the steam generat o r wi th water c lo se the nec k b y ,

the o ne hole cor k carr y ing t h e safet y tube and c o nn ect the steam
-

o ut l et pipe with the r o un d bottom flask - .

P lace in the flas k 3 00 c c o f the o r g ani c li quid t o be used

. .

together with 2 5 c c of water make a ll c o nnecti o ns t ig ht an d

. .
,

se e that c o ld tap water i s ru nning thr o u g h the condenser .

H eat both the can an d the flask the l atter b y mean s of a ,

l owflame which ma y be removed as soon as the flas k i s th o r o u g hl y

heated an d the steam no l o nger c o ndenses in i t .

I n o rder t o prevent the partial c o n de n sation o f v ap o r i n the

nec k of the flas k and the stil l hea d wrap a piece o f c lo th ar o un d ,

these parts .

R ecor d the bar o met ri c pressure an d the r oom t emperature

at the beginning and the end o f the exp er iment .

Co llect the fir st 1 0— 20 c c o f the distil l ate separate ly in an

. .

E rlenme y er flas k and as s oo n as the disti ll ate c o mes o v er regu

larly c o ll ect three 1 00 c c samples i n the graduate d c y l i nd ers
-
. . .

Watch the temperatu re carefu lly d ur ing the t ime of sample

tak ing and rec o rd the same e v er y minute f o r the d istillation ,

sh o uld be carr i e d o ut at c o nstant temperatur e Thi s wi ll be .

the case s o lo ng as t h e steam b ubb l es t hroug h th e o r g ani c li quid

at a uniform rate .

Leave the di stillates i n the gra d uates unt il the nex t l abo
r at o r
y per i o d w hen the emu l s i ons w ill ha v e chan g e d in t o clear
layers B o t h t h e upper ( aque o us) and th e lo wer l a y er in each
.

graduate are then carefu ll y measured i n c c . .

D isconnect the r o und b o tt o m flas k c ool and empt y i ts con

-
,

tents in to t h e separator y funn e l R eplace the empt y flas k a n d .

pass steam thr o ugh it re co rding o ne min ute temperature read

,
-

i n gs until fiv e consecuti v e c o nstant o bserv atio ns are o b tain ed .

.

Kn o wing the c o rrect bar o metric pressure a c o rrecti o n for the

b o ili n g points o f pure water and the mixture can be applied .

Turn Off b o th gas an d water before l ea v ing the l a b orator y .

72 LABORATORY MANUAL OF P HYS I CAL C HE MI STRY

O b s e rvatio ns an d M e asur e m e nts

S
B arometric pressure at start mm corrected v alue
. .

room temperature
ame at e nd of e xperime n t
room temperature
Ob served b oili ng po in t of mix ture ( readin gs e very minute)

Value of b oili n g poi n t of

-
m ix t tlre as derived from these
O b servatio n s

O b served b oilin g poi n t of water

-

values : b p mixture
Corrected . .

Cy l 1 Cy l
. . 2

N um b er O f c c of
. .

water c ollected
N um b er O f c c of
. .

collected

1 F rom the de ns iti es of the li qui ds for which

.
,
see T ab l e 4 ,
calculate the weight of each .
 S
E XP E RI M E NT 1 0

M IN I M U MB O IL IN G L IQ U I D
O b j e ct
To S h o w that mixtures of certain pairs of li q uids have boiling
poin ts which are lower than the boili n g points o f either of the
pure compounds .

Re fe r e nc e s
Text bo o ks

S
’

S
B igelow XX III V ap o r P ress of S o ln s p 3 09
, ,
.
,
.

Getma n VI I olutio n s p
, , ,
.

J o nes V o lu tion s p 1 83

SS
.
, , ,
’
L inco l n X V I So ln s o f L iq in L iq I I p 1 79
, ,
. .
, ,
.

M illard V olutio n s p 1 3 2

S S
.
, , ,

M organ V I olutions p 1 3 7
, , ,
.

e n ter I V olu t i on s p 8 7
, , ,
.

Walker V III V apo riz n 81 C o n den sation p 78

, ,
’
,
.

S
B riggs V I I D is t il n o f L iqui d M ix tures p ’
, , ,
. 26

E well III
,
ol u t i o ns p 1 5 7, ,
.

R o b in son ,
1 . c .
,
Ta b le 3 , Appe n dix , pp . 1 80— 1 88

1
1 t hree -
neck ed boi ling point v esse l -

I
1
See foo tno te pag e , 57 .

75
76 LABORA T ORY MANU AL OF PHYS I CAL CHEM I STRY

1 trip od
1 wire gauze
1 perforated as b estos plate
1 2 0 in ch c o n d e n s e r + r u b b e r tu b i n g
—

1 B unsen b u rne r + ru b b e r tub ing

1 thermometer (0
I graduated cylin der ( 50 c c ) . .

I liter b ottle contain in g b e nze ne

1 liter b ottle co ntaini ng methyl alcohol
F ig 1 4 gives a sketch of t h e assem b led apparatus Th e
. .

three n ecked b oilin g poi n t vessel is supported o n the wire gauz e

- -

b y mea ns of the perforated as b estos plate ( laid on the iro n

r ing) a nd co nn ected air —tight to the refl ux water cooler on the -

right Th e ce n tral ope n ing of the vess el is close d b y a ti ght

.

fi t t in g perforated cork carr ying a thermometer .

M eth o d of P roc e d ur e :
S in ce b oth b e nze ne a nd methyl alcohol are highly infl am
ma b le it is n ecessa r y to i n sure air tight co nn ectio ns especially
-

at the o ne hole cork co nn ectin g the b oil in g poi n t vessel to the

‘

- -

co nde n ser .

R e gulate the flow of tap water through the c o n de n ser .

P our 50 c c of b e nz e n e measured in the 50—c c graduate through

. . . .
,

the S ide n e c k o n the left .

5

C lose the n eck a nd determine the b oi lin gpo in t of the liquid .

I n th i s a nd all follo wing determin a tio n s the bul b of the ther

m o m e t e r S hould dip in the l iquid and the thermometer be of
such le ngth t hat the cork does no t interfere with readin gs
a b ove
R ecord th e b arometric pressure and room temperature .

H avin g o b ta ined the b oilin g poin t tur n o ff the gas wait a , ,

few m inutes un til the li q uid has suffi cien tl y cooled an d i n tro ,

duce 1 0 c c Of methyl alcohol through the S ide n eck

. . .

Close the n eck a nd determine the boili n g poi n t of this

mix ture .

30 c c of methyl alcohol
. . .
MI NIM UM BO IL I N
. G L I Q UID S 77
78 LAB ORATORY M ANUAL OF P HYS I CAL CHE MI STRY

t o the waste b ottle R i n se the flask with about 1 0 c c o f methyl

. . .

alcohol a n d after assem b lin g the apparatus as before in troduce ,

50 c c of methyl alcohol a nd determ in e its b oilin g point

. . .

R epeat the b oi li n g poin t determin ation three tim es b y

-

addin g successively 1 0 20 a n d 2 5 c c Of be nzene

,
. . .

Turn Off b oth the gas and water supply a nd pour the c o n
te n ts o f the flask in to the waste bottle D O n o t rinse the bo il .

in g poi n t vessel with water

- .

B arometric pressure : Corrected value :

R o om temperature :
L i q uid A ( b e nze n e )
Liquid B ( meth yl alcohol)

B oili n g poi n t
( u n corrected )

Added 10 cc . .

20 c c ( total
. .
3 )
0

30 . cc . . 60)

Added 10 cc . .

20 c c ( total
. .
3 0)
25 cc . .
55)

the volumes of A and B for each

the b as is of a total volume of 1 00 c c . .

the tempe rature as ordinate 5 cm ) against the volume

.

con centration ( 1 0 per cent = 1 cm ) . as abscissa .

 E XP E RI M E NT 1 1

B O IL I N G PO I NT AND VAP OR CO M P OS I TI O N
-
CUR V E
OF L IQ U ID M IX TUR E S
Obj e c t
To determin e the b oili n g poi n t a n d vapor composition -

curve for the b i n ary li q uid mix ture (max imum b oili n g point) :
hydro c hloric aci d water -
.

Te xtbo o ks

B igelow X XII I V apo r P ress O f S olutio ns p 3 0 7

, ,
.
,
.

G e t ma n VI I S olutions p, , ,
.

L i ncol n XVI S olu s of L i q uids in L i q uids I I p 1 78

, ,
’

, ,
.

M illard V S olutio n s p 1 20
, , ,
.

S e n ter IV S olu t io ns p 89
, , ,
.

’
Walker VIII V apo riz n 81 Co nde nsatio n p 7 9
, , ,
.

B riggs VI I D is t ill n O f L i q uid M ix tures p

, ,
’
,
. 23

E well I II S olutio n s p 1 5 7
, , ,
.

H ollema n ( Walker ) Te x tboo k of O rgani c Chemistr y , ,

P ar . 22, F ractio nal Distill atio n p ,

. 24

p . 1 84 ( wi th litt ref ) . .

1 thermometer ( 1 00 graduated In te n t hs of
82 LAB ORATORY MANUAL OF PHYS I CAL C H E MI STRY

use of a n as b estos mat or a wire gauz e in creases b umpin g and

for this reaso n the distil latio n S h o uld b e carried out with a b are
flame .

Adjust the flame in such a mann er th at distillation pro

c e e d s rather vigorously yet at a unifo rm rate As soon as the
,
.

thermometer h a s warmed up to e q uili b rium i e after from ,

. .
,

1 0 to 1 5 c c of dist illate have b ee n collected in the graduated

. .

cyli nder place the test tu b e la b eled D 1 at the outlet of the

,

co nde n ser a nd collect a b out 4 c c of distillate Wh ile this . . .

po rtio n is b e in g distilled read the t he rm ometer to an d record

the sam e .

Whe n e nough distillate h as been coll ected rem o ve the flame , ,

pipette O ff a 5 c c sample of t h e liquid in the fl ask ( this portio n

-
. .

n eed n o t b e measured accurately) a nd place it in the test tube

marked R 1 S top per t h e test tubes imm ediately

. .

R eplace t h e thermometer an d continue t h e distillati o n ( usin g

the same flame ) at the sam e rate as before until the therm ometer
S hows a rise of from to R eject the po rtion which has
come over duri ng thi s in terval the n collect a 4 c c sam ple o f ,
- . .

distillate in tu b e D 2 tak in g a tem peratur e readin g a nd recor d

,

ing t h e sam e as b efore R emove the flame and place a 5 c c

.
-
. .

sample from the flask in Tu b e R2 .

C o n ti n ue the Operatio n as out lined ab o ve ta king (appro xi ,

mately ) 4 c c samples of distill ate and 5-c c sam ples of residue

- . . . .

a n d recordi n g the temperature for each rise of approxim atel y ,

o n e degree until a b out 1 0 c c of li q ui d remain in the flask

,
. .
,

whe n a final sample of distill ate and residue are taken and the
final tem peratur e read .

While o ne stude n t is carrying out the di still atio n h is partner ,

determin es the H Cl co n ten ts of the samp l es b y t i trat ing the

same wi th standard ( N/ 5) alka li Th e series o f R samples .
-

shoul d b e coo led to the same temperature as the D samples -

before analysis .

Th e anal ysis is carri ed out b y wi t hdrawin g ex actl y 1 c c o f . .

sample by means of the small pipette runnin g it i n t o a 1 50 c c ,

-
. .

E rle nm eyer flask ad din g abo ut 2 5-c c of boi lin g distilled water
, . .

from a wash bottle heated over a wire gauze and titrating with ,
 BO IL I N G PO I NT AN D VAP OR CO M POS I T I ON 83

stan dard alka li ( usin g tw o drops of phen o lphthalein as i n dicator)

until the fir st permane n t pink color de v elops B efore taki n g .

a sample from a test tube rin se the pipette wi th the soluti o n

to be sampled an d re mo v e the last dr o p o f r i nse solution from
the tip b y touchi ng it wi th a piece o f filter paper E ach titra .

t ion i s run in dup licate and the resul t entere d in the record o f
Obser v ations .

When the d i still atio n i s c omp l ete r inse the di sti lli ng flask
, ,

intro d uce about 2 50 c c of distil le d w ater assemble the appa

. .
,

ratus as before and chec k the readin g Of the thermometer at the

b o i lin g point o f pure w ater R ec o rd the barometric pressure
.
,

then Obtain the true boiling po in t of water at this pressur e

from Table 2 i n the Appendix and if the thermometer does ,

not read correctl y determin e the c o rrection t o be applie d

, .

C orr ect all Obser ved temperature readings .

Ob se rv ati o n s an d M e a sur e m e nt s

c c
. . of a lk ali u s e d
Temperature s No rmali ty
Obs erv e d C o rrec te d S ampl e S amp l e Av erage
1 2
84 LABORATORY MANUAL OF P HYS I CAL CHE M I STRY
‘

B arometric pressure ,

S ame corrected mm
. .

B oilin g poi n t O f water a s fou n d

S ame as give n b y ta b le ,

1 F rom the result of the titratio n s fi n d the

. of
each sample Of distillate a n d residue a nd rec o rd t h e same in
,

the a b ove ta b le .

2 F rom Ta b le 7 in the Appe n di x find t h e percen tage of

.
,

H C l correspo ndi n g to each n ormali ty an d place these v alues

,

in the last colum n .

3 P lot o n a su f ficie n tly large scale the percentages so

.
, ,

fou nd as a b sciss a agai n st temperatures as ordi n ates Co n .

n e c t the poi n ts b y curves a n d locate the positio n of the ma x i

mum b o ili ng m ixture .

S SS
E XP E RIM E NT 12

OLU B IL ITY CURVE FOR A TE R NAR Y

O b j e ct
L IQ U I D S Y TE M OF

To determine the solu b ilit y cur v e for a ternar y s y stem of

two n o n miscible liquids ( water and b enz ene) and a third li q uid
-

( acetic acid) conso l ute with either of the tw o

1
.

Re fe r e nce s
Te xtbo o k
L in c ol n XV
La bor a tory
,

M a nu al
,
S
.
olutio n s of L i q uids in L i q uids p ,
. 1 61

B riggs X V , ,
E q u il 81 P hase . R ule p ,
. 65

S pe cia l Te xt
’ ’
F in d lay P hase R ule s , 3 d E d ,
XI V ,
S o ln s of L i q uids
in L i q uids p 243 ,
.

J o u rn a l A r t i cl e s
L in coln Jour P hys ,
. . Chem 4 ,
. p . 1 6 1 ; 8, p . 2 48 .

Apparatu s an d Che m i c al s re q ui r e d
2 iro n stan ds
2 burette holders
4 burettes
1 5 c c pipette
-
. .

1 2 c c pipette
- . .

1 1 2 5 c c E rlenme y er fla sk + c o rk stopper
-
. .

1 3 00 c c E rle nmeyer flask + c o rk stopper

-
. .

1 b ottle contain in g distilled water

1 b ottle co n tainin g be nz ene

1 b ottle co n taini n g glacial acetic aci d

88 LABORATORY MANUAL OF P HYS I CAL CHE MI STRY

(S t ud e nt A ) U sin g the 5 c c pipette introduce 5 c c o f

.
- . .
, . .

b enze ne in to the 1 2 5 c c E rlenmeyer flask then add 1 c c

- . .
, . .

of water from o n e b urette a nd from another b urette little by , ,

li ttle glacial acetic acid un til after vigorous S hakin g a clear

,

( no n clou d ) solutio n is Ob tained which is saturated with

- y

respect to t h e three compo ne n ts .

R ecord the volumes added .

Ad d 2 c c of water to the li q uid shake vigorously a nd

. .
,

repeat the additio n of acetic acid u ntil the mi xture agai n b ecomes
homoge neous .

Add su c cessively 3 then 4 5 and fi n ally 6 c c O f water and

, ,
. .

in each c ase add e n ough acetic acid to produce a clear li q uid .

R ecord all results .

(S tud e nt B ) B y mea n s of the 2 c c pipette introduce 2 c c

.
-
. . . .

of b e nz e n e i n to the 3 00 c c E rle nm eyer flask Ad d 2 5 c c Of

-
. . . . .

water from o ne b urette and then from a seco n d enough glacial ,

a c etic acid to produ c e a clear homoge neous li q uid after shaki n g .

Th e operatio n is repeated b y addi n g successivel y 5 more

portio n s of 2 5 c c of water ; in each case the e xact volume of
. .

aceti c acid necessary to produce a clear n o n c lo ud y solutio n is ,

reco rded .

Ta b ula tio n of R e sul t s

B e nz e ne Water Ac etic A id c

Add e d N T ta l
o Add e d T t al
o

O
O

A
M
O

25

A dd e d 25 T ta l
o

25

2S

25

2S
 S S
E XP E RIM E NT 1 3

TRAN I T I O N P O I NT S I N TH E O L I D S TATE

O b j e ct
To determin e the tran sitio n poin t of a nh ydrous
sulphate by the thermometric method .

Re f e r e nce s
Text boo ks
B igelow XXI V apor P ressure p 2 9 2
, , ,
.

Jo n es IX Chem D y n 81 E qu il p 589

S
. . . .
, , ,

L in col n XVI I P hase R ule p 1 9 0

, , ,
.

e n ter V II I H e t e re o ge n e o us E q u il p 1 83

S
. .
, , ,

Walker X Phase R ule p 1 0 1, , ,

.

Washburn V C r y stallin e tate of Aggregatio n p

, , ,
. 66

La bo ra to ry M a n u a ls :
B riggs XV E q u il 81 P hase R ule p 6 1
, ,
.
,
.

E well V II C hem , S tatics p 2 76

, , ,
.

F in dla y X V D e t e rm n of Tran s P t s p 3 08
, ,
’
. .
,
.

F ir th V I D e t e rm n of Tran s P ts p 3 5
, ,
’
. .
,
.

Getma n X V C hem Kinetics p 248

S
, . .
, ,

Gray E x 1 2 D e t e rm n of Tran s P t s p 60
,
.
,
-
’
. .
,
.

Roth (Camer o n) V II C hem tatics 81 Dy n amics , ,

.
,

p 1 04 .

’
F in dla y s P hase R ule , 3 d E d ,
p .
34 1 .

Appar atu s an d Ch e m i c al s r e qu r e d : i
1 iron sta n d
1 clamp
1 iron ring
1 large copper o r iron cruci b le ( dime n sions 8 —
10

1 test t ube ( len gth 1 5 cm diameter cm ) .

,
.
92 LABORATORY M ANUAL OF P HYS I C AL CHEM I STRY

1 b ottle co n taini ng anhydrous s odium sulphate

1 co n tai ner with dr y sand

FI G . 15 .

arrangement is readily un dersto o d from F ig 1 5 Th e

Th e . .

metal cruci b le is supported o n an iron rin g and contai n s dry

held in a central position i nside the tube by a clamp

m o m e t e r is ,

in such a way that the bul b is completely immersed in the finel y

M e th o d of P r oc e d ur e
 S SS
E XP E RIM E NT 1 4

P HA

O b j e ct
E D IA G RAM FO R A
OF M ETAL
TWO -

S
C O MP O NE NT Y TE M

To determi n e b y mea n s o f coolin g

e q uili b rium in a b inary all oy .

Re f e r e nce s
Te xtbo o ks
’
B igelow XX I V ,
of S ol n 8,
P rocess
p 3 49 1
.

Getman XII I H eteroge neo us E q uil p

, ,
.
, .

Lin col n XIX So ln s of S o lids in L iquids II p 2 1 1

’
.
, , , ,

M illard IX H eteroge n eous E q u il p 2 7 8

, ,
.
,
.

S enter V I I I H e t e re o ge no us E q uil p 1 90
, ,
.
,
.

Walker XI Allo y s p 1 1 2
, , ,
.

La b ora to ry M a n ua l :
E well V II C hem S t atics p
, ,
.
,
. 271

small iron rings

B uns en b urne rs + ru b b e r tub ing
clamps
thermometers ( ni trogen fille d ) graduated to -

B attersea cruci b les D (diameter 6 cm l ength 1 0 .

,

numbered from 1 to 6 co n tainin g respect

iv e ly
200 gr ams o f cadmium
1 60 grams o f cadmium + 40 grams o f b ismuth
1 20 grams of cadmium grams of bismuth
 P HA SE G
DI A RAM FOR A TW O COM PONENT SYSTEM -
95

O ne uni t of t he
apparatus is S h o wn i n F ig 1 6 Th e metal . .

o r allo y un d er obser v at i o n is placed in a B a ttersea crucible an d

co v ered with a thi n la y er o f charcoal t o pre v e n t o xidatio n Th e .

crucible is supporte d in an iron ri ng an d heated o ver a B unsen

burner Th e thermometer c o vered at the top with a piece of
.
,

heavy rubber tubi n g mo v es freel y through a perf o rate d c o r k

,

he l d b y a c l amp and sin k s b y

it s o wn w eigh t in the meta l ( o r
al loy) as s oo n as the l atter fuses .

S
M e th o d of P r o ce d ure

tu d e n t A c o n fines his o b se r
v a t io n s to s amples 1 2 an d 3 ;
,

student B t o samples 6 5 and 4 ,

.

B are ly me l t the metal in cruci

ble and see that the bulb of
the thermometer is imrh e rse d i n
‘

the center Of the mo l ten metal .

B e careful t hat t h e mercury does

n o t rise ab ov e I f it d o es
tend to r i se above th i s limit im ,

mediatel y withdraw the t her

m o m et e r and d o not return it t o
the melt until the temperature
h a s fa l len to bel o w
R emo v e the flame allow the ,

s y stem t o c oo l with o ut inter

ference o f any kind ( a v oid air
d rafts " ) and rec o r d temperature
readin gs at 1 5 sec o n d in terv als
-

°
ov er the range 3 40 ,
FI G 1 6
Again melt t h e metal tak ing
°
temperature readin gs from 1 3 0 3 AS so o n as the th er
—

m o m e t e r reaches the latter temperature remove the thermometer .

When the mercur y h a s fallen to below 1 00 rem o ve any °

a dher ing metal by dissolvin g i t i n nit ri c aci d i n or d er t o pre vent

a change in the compos i tion of the nex t melt .

I n a s imi lar manner o btain c o o lin g ( an d heatin g) curv e d ata

96 LABORATORY M ANUAL OF P HYS I CAL C HE MI STRY

fo r alloys in cruci b les 2 and 3 ( 5 an d

the In
° °
b etween the 3 00 —
1 20 as the

at a much lower temperature t ha n the pur e metals .

S ampl e 1 or 6 2 or 5 3 or 4

On C o o l i ng
 E XP E RI M E NT 1 5

M O N O M O L E CUL AR R E ACT I O N : I NV E RS I O N

Obj e ct
O F CANE UG AR S
To determ ine the reaction velocity for the mo nomo l ecular
reactio n : the in versio n of ca ne sugar .

Te xt b o o ks .

B igelow XX V Vel of C hem R eactio n s p 3 53

, ,
. . .

G etm an XIV Chem Kin etics p , ,

.
,
.

Jo nes IX Chem D yn 81 E q u il p 53 1
, ,
. . .
,
.

L i ncol n XXXVI R ate O f Chem R eactio ns p 48 7

, ,
.
, .

M illard X Kinetics of R eactio n s p 2 9 9

, , ,
.

M organ VI II C hemical Cha nge p 2 8 2

, , ,
.

S e n ter IX Vel Of R eactio n p 2 29

, , .
,
.

Walk er XXV R ate of Chem Tra ns p 2 86

, ,
.
,
.

Wash b ur n X X I C hem Ki neti cs p 2 70 , ,

.
,
.

E well ,VI Chem Kin eti cs p 23 2 ,

.
,
.

F i ndlay XI I Vel of Chem R eactio ns p 2 6 2

, ,
. .
,
.

F irth XVI Vel O f Chem R eactions p 1 40

, ,
. .
,
.

Getman XV Chem Kin etics p 243, ,

.
,
.

G ray E x 2 8 Vel O f I n v Of C an e S ugar p 1 2 2

,
.
,
. .
,
.

R oth ( Cam ero n) V I I Chem S tatics 81 Dy n amics , ,

.
,

p 1 06 .

Apparatus an d Ch e mi cal s r e quir e d

1

1 s o dium light
1 jacketed po la rirne t ric tub e 20 cm lo ng .

1 coiled copper tu b e 1 meter long in tern al diameter , ,

5 mm .

1 iro n stand
 M ONOMOLE CULAR RE A CTI ON 99

2 B unsen burners + rubber tub in g

1 bottle wi t h three holed stopper carr yin g 2 gl ass tubes
-

a n d 1 therm o meter (0

1 2 5 c c pipette
- . .

2 1 00 c c beakers
- . .

1 stoc k bottle con ta i ni ng n o rma l h yd r o ch l or i c acid

I stock bott l e co n tain in g a 2 0 per cent sugar so l u
ti on preserv ed b y a tin y cr y stal of camphor .

Th ep ol ar imeter ( drawn schematicall y) jack eted tube and , ,

sodium light are shown in F ig 1 7 Tap water is passed at . .

a regulated rate through a c o iled copper tube heated b y a care

full y re gulated flame nex t through a o n e-liter b o ttle con tain
,

ing the thermometer (n o t S h o wn in the figu re ) th en through

the jack eted polarimeter tube an d thence t o waste ,
.

1
A thoroughl y satisfactory source of sodium light c o nsists
o f a sma ll alundum crucible ( R A 3 60) ab o ut o ne th i r d ful l of .
-

Na Cl heated ov er a M ek er burner
,
.

M e th o d of P r o ce d ur e °

B rin g the water circulat ing thr o ugh the jack eted tube to
°
3 0 and mai n ta i n it there b y co n stant watchin g .

Dr y the p olarimeter tube .

P lace the s o dium flame about 20 cms from the polariscope .

,

light the gas remo v e the tube fr o m i ts rac k and se e that the
,
.

p o lariscope is in adjustment .

Pl ace 2 5 c c o f the 20 per cent s ugar so l ut i on i n one beak er

. .
,

a n d an e q ual v olume ( use pipette both times ) o f n o rma l h y dr o

chloric acid in the other B rin g the temperatur e o f each t o

.

mix the so l uti ons and fil l the polar im eter tube takin g care ,

to elim i nate an y a ir bubbles whi ch might te n d t o collect therein .

Pl ace the tube in position and at o n ce ta k e a readin g n o t in g ,

the time at which the readin g was tak en .

F o r t h e first twe n t y minutes take o n e m inu te rea di n g s for -

,

the nex t twen t y two -minute re adin gs and for the nex t sixty
, ,

fiv e minute rea di n g s o n the D o larim e t e r record ing a l so t ime

-
,

(and temperature) .

1
F al e s 81 Mo rrell Jo ur Amer C h em Soc 43 p 1 6 29
, . . . .
, , .
1 00 LABORATORY MANUAL
1 02

0 0 0 0 0 0

0 0 0 0 0 0

1 . P lot b served a ngles

the O large agai n st
the times ( 5 m in = 1 large divisio n) as a b scissae and draw a
.

smooth curve through the poin ts .

2 .S elect four represe n tative poin ts o n the curve and cal

c ulate the velocity co n sta n t for these poi n ts
.
1 06 LABORATORY MANUAL OF P HYS I CAL CHEM I STRY

Apparatu s an d Ch e mi cal s r e qu ire d

1 thermostat ,

1 iro n sta nd
2 b urettes
1 burette holder
1 5 0 c c-
pipette . .

1 2 5 c c pipette
- . .

1 1 2 5 c c E rle nmeyer flask wide mouth

-
,

2 2 50 c c graduated flasks
- . .

I 1 000 c c flask -
. .

1 1 00 c c b eaker-
. .

1 b ottle of ethyl b romacetate

1 stock b ottle of h undredth normal i o dine soluti o n
1 stock b ottle of six tieth n ormal sodium thiosulphate
solutio n
1 b ottle O f starch i ndicator solution
M eth o d o f P r o ce d ur e
S ecure from the instructor a small glass stoppered vial con -
,

l
taini ng no t over 0 5 gram of ethyl b romacetate Open it u nder
.
,

water in a sma ll b eaker and tran sfer to a clean 2 50 c c grad

, ,
-
. .

uat e d flask R in se the beaker wi t h water and add the

.
,

washings to the graduated flask M ak e up t o 2 50 c c and . . .

,

place the flask in the the rmostat .

F ill the other 2 50—c c flask to the mark wi th s odium t hio . .

sulphate solutio n and place it in the thermostat ,

.

Wh e n the temperature of both solutions h as reached

the two li q uids are mixed in the 1 000-c c flask ( the time of . .

mix in g b eing take n) the flask is S hake n and p l aced in the ther , ,

m o st a t .

the e nd of five m inutes ( counted from the t ime o f m ixin g)

At
remove 50 c c from the reactio n flask and titrate ra pid ly with
. .
,

the hundredth normal i odin e solutio n us ing starch as indicat o r , .

At the e nd of 1 0 1 5 2 5 40 60 and 90 min utes ( fr om the , , , , ,

start o f the reactio n) wi t hdraw 50 c c from the flask and titrate ,

. .
,

run i n to the titratio n flask in each instance .

The es ter has s tro ng l ac rymato ry pro pert ie s

1
.
 B I MOLEC ULA R RE ACTI ON 1 07

B etween the la st tw o t i trat i ons d eterm ine the i n itial c o n ,

centrati on of s o dium thio su l phate in the flas k by withdrawing

2 5 c c from the stoc k b o ttle a n d titrati n g with iodine
. . Wh y ,
.

with draw 2 5 c c here instead o f the 50 tak en f o r the other

. .
,

titrations " E xpress thi s c o ncentration in c c o f the iodin e . .

require d .

v
r

After at l east fi v e Or S ix h o urs o r better s til l a t t h e start , ,

o f the nex t laborator y peri o d titrate 50 c c o f the liquid remain ,

. .

in g in the reacti on flas k Th e reaction bei n g presum abl y c o m

.

p le t e at this tim e the vol ume o f iodin

,
e s o luti o n required for this
titrati on represen ts the ex cess of thiosulphate origin all y prese n t
i n the mix ture Th e v alue o f this titratio n theref o re su b
.
, ,

tracted fr o m the value of the titration of the 2 5 c c of thio . .

sulphate withd rawn from the stock b o ttle gives the i n itial ,

concen tration Of the ethyl bromacetate solution presen t in 50

c c of the mix ture expressed in c c of iodin e solution
. .
,
. . .

O b se rvati o ns an d M e a sur e m e nts

S
c c iodin e
. .

Th e solutio n s were mix ed at

1 st ample titrated at
( C ( C
2d

3d
4t h
5t h
6t h

7t h
Titration of 25c c stock thiosulphate
. .

mix ture at end of reactio n

U sin g the in tegrated e q uatio n for the velocit y c o n stan t

of bimolecul ar reaction s calculate the value of k for each ,

mi xture expressin g the concentratio n in c c of i odine solution

,
. .

use d .

2 Al so calculate the v alue of the consta n t expressin g the

.
,

co n cen tratio n s of the reacti n g mix ture in moles per liter .

3 F ind the time necessar y to conv ert half Of the ester

. .
 E XP E RIM E NT 1 7

H E AT OF NE U TRAL IZ ATI ON

O b j e ct
To d etermine the heat of neutraliz at io n of an ac i d b y a
base .

R e f e r e nc e s

Text bo o ks

B igel o w XX V II Th e rm o ch e m Data p 406

, ,
.
,
.

Getman ,
p .

J o nes V I Thermochemistr y p 333

, , ,
.

L inco ln XXX I V The rm o chemi str y p 43 1

, , ,
.

M illard V II Therm o chemistr y p 206

S
.
, , ,

M organ V II Therm o chemistry p 2 2 9

, , ,
.

e n ter X I E q uil i n E lectr oly tes p 283

, ,
.
,
.

Walk er XX IX App licati o ns o f the D iss n

, ,
’
Theor y ,
P 33 6
Washburn X I X , ,
Th e rm o ch e mis t ry , p . 243

La bo ra to ry M a nu a l s
B riggs X V II Therm o chemistr y p 84
, , ,
.

E well I V Therm o chemistry p 1 9 3

, , ,
.

F in dl a y X III Therm o che m istr y p 2 78

, , ,
.

F irth X II Th e rm o ch e m M eas p 74
, ,
. .
, .

Getman V I I Calo rirn e t ry p 1 07

, , ,
.

Gray E x 1 8 H eat of Neut p 80

,
.
,
.
,
.

P ring P art I C a l orimetr y p 2 3

, , ,
.

R o th ( C ameron) IV Thermochemi stry , , ,

P 1 33
1 12 LABORATORY MANUAL OF PHYS I CAL CHEM I STRY

Appar atus an d Ch e mi cal s re quir e d

1 mixture cal o rim eter
1 the rm ometer (0 graduated to te n ths of a degree
1 B eckma nn the rmometer
2 2 50 —c c graduated flasks cali b rated to deliver
. .

1 readi ng glass
1 stock b ottl e wi t h N/4 sodium hydro xide
1 stock b o ttle with N 4 hydr o chloric acid

Th e calor im etri c vesse l i s represented in F ig 1 8 and c o n .

,

sists of a highly po lished cylindrical metallic vessel with card

b oard 01 e b o nite cover through which pass the B eckm ann
thermometer the stirrer and a glass tu b e for in trod uci ng the
, ,

solutio n from the uppe r vessel Th e upper vessel carries a .

q uick ope ni n g valve at the b ottom

-
Th e calorim etric vessel .

is surro unded b y three oth er cylin drical vessels a nd the a nn ular

space b etwee n the two outer cylinders is filled with water Th e .

upper vessel c a n b e swu ng in to positio n for dischargi n g its

co n tents int o the ca lorim eter .

M eth o d o f P r o ce d ur e

P lace c c of fourth norm al sodium hydro xide accurately

2 50 . .
,

measured in o ne graduated flask i n to the ( lower ) calorim etric ,

vessel P u t t h e covers the b rass stirrer an d the B eckmann

.
,

thermometer in positio n after settin g the mercury column so

,

that it reads a b out half a degree from the b o ttom Of the scale
whe n placed in t h e alka li solution .

P our a b out 2 60 c c of four th n ormal hydrochlor i c aci d int o

. .

the upper vessel the n run it b ack into the flask

,
.

M ak e up t o exactl y 2 50 c c I n this wa y the error d ue t o

. .

the acid adherin g to the wa lls of the upper vessel when dis
char gin g the 2 50 c c into the calorimeter is eliminated
. . .

R eturn the accuratel y measured acid to the upper v essel

and place the o rdinary th erm ometer in thi s solution .

S ee that b oth th e acid and the base are when p l aced in the ,

upper and lower vesse l at appr oximately the same temperature

,
.
1 14 LAB ORATORY M ANUAL OF PHYS I C AL C H EM I STRY

F inall y c o mpare b oth the rm ometers b y placin g the ordin ary

t herm ometer e t to the B eckman n in the lower vessel and
n x ,

wh ile stirrin g con sta n tl y take the readings o n bo t h altern atel y

,

for at leas t three mi nutes .

I n order to fin d the water equivalent o f the calor imeter a nd

stirrer weigh the calorimeter a nd the b rass stirrer o n a n ordi
,

nar y b ala n ce ( to te n ths of a gram ) b o t h bein g thoroughl y dried

,

b eforeha nd S ee Ta b le 8 Appe ndix for S pecific heats

.
, , .

Th e water e q uivale n t of the porti o n of the B ec kmann ther

m o m e t e r immersed in t h e liquid is readil y f o und b y water
displaceme n t Co u nterpo ise a tall n arrow beaker o f water o n
.

the ordin ar y b al ance by mea ns of another b eaker of water .

C arefull y clam p the thermometer a nd suppo rt i t o n an iron

sta nd s o that o nl y the bul b is immersed Th e weight t o b e

S
.

added o n the other ba l ance pan represe n ts the v olume of th e

water displaced by t h e glass and mercury o f the bulb ince .

1 c c of glass h as appro ximately the same water equi v ale n t

. .

as 1 c c of mercur y . . it

S
is o n l y n ecessar y to multipl y the weight of the displace d water
by to obta in the water e q uivale n t of t h e bul b .

in ce t h e stem of the therm o meter above the bul b i s also

partl y in the liquid dip t h e thermometer as far in the water
,

of the beaker as it was imm ersed in the so l ution in the c alo rim
eter and again determine th e weight of the water displaced .

O nl y one fi ft h of the d ifle re nce of thi s and the pre vious

-

weight is so lid glas s ( th e stem being ho ll ow) ; therefore take

o n e fifth of the d if
-
f erence o f bo th weighings m ultipl y th i s b y,

an d add this to t h e water e q uivale n t of the b ul b Thi s .

gives the total water eq uivalen t of the immersed po rtion of the

B eckm ann thermometer .
 H E A T OF NE UTRAL I Z ATI ON 1 15

R eadings o n
o r di nar y therm meter
o

eter (l o wer v e ss e l )
At start
'

30 se c o n d s
1 m i nute

1 50seconds
3 mi n utes
2 1 0 sec o n d s

4 m inutes
27 0 sec o nd s
5 m inutes
6 m i nutes
“

7
8

9
10

II

1 2

1 3
1 4
1 5

C omparison of both t hermometers

 1 . P lot
temperatures as ordin ates 10 cm ) against .

times as ab scissae ( 1 m in 1 . recordin g al l values in terms

of the B eckm an scale B y means of a straight line project the
.

las t seve n or eight read in gs back to the perpendicular for th e

tim e of mix in g and call the temperatur e correspo n din g to this
intersectio n the t ru e temperature attain ed on mix i n g .

2 .Takin g as 13 and tA t h e i n crease in temperature of b ase

a n d acid respectively a n d assumi n g that the specific heat o f
,

the dilute acid an d b ase is t h e same as t hat of pur e water n amel y

1 we have

H eat a b sor b ed b y acid 2 50tA

H eat a b sor b ed b y b as e + ca lo rim e t e r ( 2 50 + W) t3
H eat li b erated by n eutra lization 2 t
5 A
0 2 5o l g WtB ,

represe n t in g b y W the water e q uivale n t of c a lo rim

eter stirrer and imm ersed portio n of B eckmann
,

therm ometer .

3 . Co n sideri ng
the fact that o nly 2 50 c c of a fourth norma l
. .

b ase a nd a c id were u s ed t h e result o b tai n ed a b ove must b e

,

multip li ed b y 1 6 to o b tain the molar heat of neutralization .

 E XP E RIM E NT 1 8

H E AT OF C O M B US TI O N

O b j e ct
TOdetermin e the heat Of com b ustio n of a give n carbon
compo un d .

B igelow XXVII Th e rm o c h e m Data p 4 1 6

, , .
,
.

G e tman XI Thermochemistry p
, , ,
.

Jones V I Thermochemistry p 3 2 7
, , ,
.

L i ncol n XXXIV Thermochemistr y p 4 1 8

, , , .

M illard VI I Therm ochemistr y p 1 9 8

, , ,
.

S e n ter VI Therm ochemistry p 1 4 5

, , ,
.

Walk er XIII Th e rm o c h e m C ha nge p 1 33

, , .
,
.

Washbur n XIX Therm ochemistry p 24 2

, , ,
.

E well , I V Thermochemistry p 1 9 3
, ,
.

F in dl a y X I II Thermochemistr y p 28 5
, , ,
.

F ir th XI I Th e rm o ch e m M eas p 79
, ,
. .
,
.

Getman V I I C alorimetry p 1 1 3
, , ,
.

Gray H eat of C ombustio n p 85

, ,
.

P ring P art I C al orim e t r y p 3 4

, , ,
.

Traube ( H ar di n) ,
XV ,
The rmochemica l C ons tan ts ,

p . 1 41
HEAT OF COMBUSTI ON 1 19

FI G . 19 .
1 20 LABORATORY M ANUAL OF PHYS I CAL CHEM I STRY

1 stan dard com b ustio n bom b calorimeter (oxygen

S
t ype) wi t h accessorie s 1

ample b ottles co n tai n i n g pure cane sugar b enz oic ,

acid a n d n aphthale n e for standardization pur

2
poses .

S ample b ottles con tain in g organic compounds the

heat O f com b u s tio n of which is to b e determin ed .

FGI . 20 .

F ig 1 9 and F ig 20 S how views of the E merson b omb c alo rim

. .

eter which is widely used in this coun try for the determination
o f the heat value of c ok e fuel o il g as o line etc
, , ,
.

v
1
a s mu c h as co mpl ete ca lo rimetric o utfi t s are o b ta i na bl e fro m d ealers a
In

v
minute c ata lo gue f eq ui pmen t is o m i tted F r c areful w rk t h ea diab atic c a l rim
o . o o o

eter eq ui pped w i th acu um wall ed " ac ket is preferabl e b ut mo s t l a b o rato ri e s

,

wo uld hesi tate t o u se so expe nsi e a nd fragil e an apparatu s wi th b e gi nners The.

 1 22 LAB ORATORY MANUAL OF PHYS I C AL CHE M I S T RY

Pl ace the co vers in po siti o n and clamp the thermometer

( which S hould have a cali b ratio n certificate) with its b ul b
immersed at least 4 inches In case a B eck mann thermometer
.

is used it S hould be se t s o that the mercur y thread stands

near the b ottom of the scale .

After the stirrin g outfit has been in operatio n for fi v e or six

minutes take o ne min ute readin gs on the thermometer
,
-
.

When 1 0 cons ecutive readin gs have bee n Obtain ed ignite ,

the material in th e b om b b y closing t h e firin g switch Thi s .

S houl d b e done exactly o n the min ute an d a note made Of the

time of fir ing .

Th e tempe ratur e wil l r i se rap i dl y dur in g the n e x t few min ute s

C ontin ue to take min ute readin gs un til at least 1 5 observatio n s
have bee n made after the m a ximum temperature is reached
and the chan ges per minute are regular and ver y small .

Whe n t hr ough wi th the run remove the b o mb replace it

, ,

in t h e holder and graduall y allow t h e products of com b ustion

,

to esca pe through the valve U n screw the top of the b om b and

.

note wheth er t h e sam ple was completel y burned Also se e .

whe t her the iro n wire was completel y o xidized or o nly partly
,
.

An y remaini n g pieces of iro n may b e collected a nd weighed

a n d this weight su b tracted from the weight of iro n taken .

B Determi natio n of heat of com b ustio n for an assig n ed

.

car b o n compou nd .

P repare a ta b let co n ta in i n g about 1 gram o f the ( solid ) s ub

sta nce under in vestigatio n and weigh it accur atel y .

F ollow the same directi o n as outlin ed un d e r A a nd record

the data Obtain ed in the S pace left Ope n for that purpose .

C ar efully Clean and dr y the bom b before leavin g the room .

O b servation s an d M e asurem e n ts
A . S u b sta nce used
Thermometer used NO ,

Vol ume of water used temperature of water ,

We i ght Of i ron w ire use d
Temperature Temperature
1 24 LABORATORY M ANUAL OF P H YS I CAL CHE MI S T RY

C .

of water Of water ,

C .

Weight of iro n wire used

Tim e
 E XP E RIM E NT 1 9

H E AT OF SOLU T I O N

Ob j e ct

To determ in e the heat Of solution Of a given sal t .

Te xt b o o ks

B igelow XXVII Th e rm o c h e m D ata p 4 1 3

, , .
,
.

G etma n XI Therm ochemistry p

, , ,
.

L in c oln XX XIV The rmochemistry p 4 2 7

, , ,
.

M illard VII Thermochemistry p 20 6

, , ,
.

M organ VII The rmochemistry p 2 1 6

, , ,
.

Walker XIII Th e rm o c h e m Change p 1 3 7

, , .
,
.

Wash b ur n X IV S olutions IV p 1 7 5
, , , ,
.

La b o ra to ry M a n ua ls

B riggs XVII Thermochemistry p 8 2

, , ,
.

E well IV Thermochemistry p 1 8 7
, , ,
.

F in dlay XI II The rmochemistry p 2 83

, , ,
.

F irth X II Th e rm o c h e m M eas p 78
, ,
. .
,
.

Getma n VII C alorimetry p 1 09

, , ,
.

G ray E x 1 9 H eat of S olutio n p 8 2

,
.
, ,
.
1 30 LABORA T ORY M ANUAL OF P HYS I CAL

I
FG . 21 .
 H EAT OF SOLUTI ON 1 31

M e tho d of P r o c e d ur e
Assemble the apparatus Ob se rv m g care that the stir rer
,

Operates freel y a n d does n o t strike the walls of the cy l inder .

F ill the D ewar cyli n der with 7 50 c c o f water measured out in

. .

i
the g raduated flask Th e temperature of the water should be
.

about o n e degree (n o t more " ) below room temperature .

Weigh out su ff c ien t finely powdered salt ( assigned f o r the

e xperim e n t) to give 1 mole Of salt in 200 moles Of water place ,

this amoun t in the thi n walled test tube an d suspen d the latter
-

in the water Of the vacuum cylin der .

C lamp the B eckmann thermometer i n place after havi n g ,

S
se t the mercur y thread S O that it stan ds midway on the scale
when the bulb is im mersed in the water .

tart the stirrer and test the electrical co nn ectio n s by closin g

the switch for an in stan t Th e curren t should b e e q uivalen t
.

t o an expenditure of about 5 watts .

After a b out 5 min utes comm e n ce to rec o rd o n e mi n ute read -

i n gs of temperature and co n tin ue un til 5 readin gs of co n stan t

,

di ffere n ce have bee n obtain ed On the n ex t full minute close

.

the heatin g switch and record half min ute ammeter readin gs -

a nd o n e —minute temperature readi n gs .

Al l ow the current to pass u n til the temperature has risen

about o n e d egree stop o n the full min ute a n d remove the copper
, ,

l eads from the mercur y cups .

After the curre n t has bee n i nterrupted co n tin ue the temper

ature readin gs f o r t e n more mi n utes .

At the e n d of this period quickl y lift the test tu b e out O f the

W ater an d S ha k e the salt i n to the c y li n der n oti n g the ex act ,

time at wh i ch the transfer was made .

R eplace the empt y tu b e immediately and co n tinue the

o n e mi n ute temperature readi n gs for at least t e n min utes
-
.

S t o p the motor and remove the heatin g coil from the solutio n .

O b se rv ations and M e a s ur e m e nt s :

S
Volume of water used c c T emperatur e . .

R oom temperature
alt used weight Of salt g .

R esistance of heatin g coi l . ohms .

 S S S S
E XP E RIM E NT 20

AD O RP TIO N O F D I SSOL V E D UB TANC E

B Y CHARC OAL
Obj e c t
To study the adsorption of acetic a cid b y charcoa l and to
te s t the validity Of the adsorptio n e q uatio n :
"
x= k y -

S
Te xt bo o ks

B igelow X V II I oluti o ns III p 24 1

, , , ,
.

G etman X Coll oids p

, , ,
.

L in co ln XXXV Colloid Chem p 4 54

, ,
.
,
.

M illard IV S o lid S olutions p 1 0 7

S
.
, , ,

S e n ter XII Coll S o ln s : Adsorption p 3 24

, ,
.
’
,
.

Washbur n XXV Dis perse y stems p 3 64

, , ,
.

B riggs X VI
, ,
Colloid C hemistry p ,
.
73

Arrhe nius , Th e o ri es
Ads ,
p 55 .
of S o lutions L ect ,
.
4, P hen o f
.

B ancroft Co lloid C hemis tr y III Ad s fr om

,
Applied , ,
.

So lu t io n p 1 00 ,
.

H atschek L ab M anual of E lem C oll o id C hemistry

,
. .
,

XVII I D e t e rm n o f an Ad s Isotherm p 1 1 6
,
’
.
,
.

VII ,
Ads o rpti o n , p . 1 04
b e measure d very Carefully and ad d ed slowly so as to allow t h e
li q uid in the burette time to drain .

S topper the flasks and shake the same successively starting ,

wi t h NO 6 for at least 1 0 mi n utes

.
,
.

P ipette Off 1 0 c c of the stock solutio n of acid place the same

. .
,

in a 1 00 c c b eaker ( allowing the pipette to drain for 2 5 seco nds ;

-
. .

this same time lim it shoul d b e o b served in all the subseque n t

operatio n s in taki ng 1 0 c c samples) add a few drops of phe nol
-
. .
,

phthale in a nd titrate with the te nt h n ormal alk ali in the seco nd

b urette Th e e nd po in t is reached when a faint p ink color
.

persists o n S hakin g Always titrate to this same pi nk color

,
. .

R epeat the titration t wice Th e determin a t io ns should check .

to within cc . .

F ilter the co n te nts of flask No 6 into a dry and clea n wide .

mouth E rle nmeyer flask ( also la b eled 6) a nd titrate 2 (or 3 )

1 0 c c samples ( check i n g to
-
. . c c ) as directed a b ove . . .

F ilter th e conte n ts of flask No 5 next and t ake 2 ( or 3 ) .

1 0 c c samples
-
. . Titrate as b efore
. .

F rom t h e filtrates of flasks No 4 and NO 3 withdraw two . .

2 0 c c samples ( usi ng the 1 0 c c pipette ) an d titrate a s before

-
. .
-
. . .

F rom the fil trates of flasks NO 2 and No I withdraw o ne . .

4 0 c c sample an d titrate t h is sample very carefully as o n ly

-
,
. .

very little alkali will b e re q uired and no t enough solution is ,

left to repeat the titration .

O b se rvati o ns and M e a sur e m e nt s

Charcoal used taken from bottle labeled
Qua n tity used grams Volume of li q uid 48 c c .
,
. .

Titrations :
S to ck No 6 No 5 No 4 No 3 No 2 No . . . . . . 1

bo ttl e

solutio n and No s . 6 a nd5 by for No s .

4 and 3
by and fo r No s . 2 and I b y
 AD SORPTI ON O F D I SSOL VE D S UB STA NCES 1 39

1 . Tabulate the resu l ts O btain ed ab o ve i n the f o ll o wi n

g

d
y
C o nc en trat io n o f s o l u
I ni t i a l c o nc n e trat io n t i o n at equ ilib r i um Am o u n t a dso rb e e x
in c c
. . of N a lk . in c c o f
. . N a lk . pre ss e d in c c o f
. .

fo r 4 8 c c . . o f so l . fo r 4 8 c c
. . of N a lk .

so l ut io n

2 P lot
. the data Ob tai n ed from columns 2 and 3 o n cr o ss
section paper ( choosing proper Un its) ; the equili b rium c o neen
t ra t io ns (y) as abscissae agai n st the amou n ts absorbed (x)

3 C alculate the values f o r l og y and l o g x and plot these

.

values on a sufficien t ly large scale the logs y as ordin ates an d ,

"
the logs x as abscissae I n case the ads o rption equation x = k y
. .

holds the 6 p o in ts wi ll lie appro xirn a t e ly on a straight lin e

S
.
,

Draw the straight lin e j o i ni n g these points and derive fr o m this

lin e the v alues for n and k ubstitute the values thus obtained
.

in the equation and calculate for each value of y the corresp o nd

I n g v alue o f x T a b ulate the results in the f o ll o wi n g ta b le :
.
 E XP E RI M E NT 21

CO ND U CTIVI TY AND D E GR E E OF I O N IZ ATI O N

Ob j e ct
Todetermi n e degree o f dissociati on b y the conductivity
method a nd to verify O stwald s dilutio n law for weak electro
,
’

lytes .

Text bo o ks

B igelow XXV I II Th e Quantity F actor p 43 7

, , ,
.

G etma n XV E le c t r Co nducta n ce p
, ,
.
,
.

Jo nes VI I E le c t ro c h e m p 3 7 7
, ,
.
,
.

L in coln XXVI I E le c t r Co n ductan ce p 3 1 1

, ,
.
,
.

M illard VI S olu s o f I o nized S u b s p 1 64

, ,
’

,
.

M orga n IX E le c t r o c h e m p 3 9 6
, ,
.
,
.

Senter X E le c t r Co nducta n ce p 2 54
, ,
.
,
.

Walk er XXII E lectrolytes 81 E lectrolysis p 243

, , ,
.

Wash b ur n XVII Co n ductan ce 81 Degree of Io n izatio n

, , ,

p 21 2
.

B riggs VI II D issociation p 2 9
, , , .

E well VII I E le c t ro c h e m p 2 7 9
, ,
.
,
.

F in dlay IX C o n d Of E lectrolytes p
, ,
.
,
. 1 65
F irth XI V
, ,

Getman X , ,

P rin g , P t . 1 ,
 CON D UCTI VI TY AN D D E REE OF I ON I Z A TI ON G 1 43

therm o stat capable o f regulation to within

,

co n duc tiv it y cell ei t her the w ell kn o wn Arrhen ius

,
-

cell or a s imple immersion t ype with so called -

di ppin g electr o des

Kohlrausch c o nducti vi t y brid g e o r S li de wire bridge
resistan ce b o x
small high frequenc y in duct io n c oil
,
-

telephon e receiv er
batter y o f 2 dr y cells
feet of i n sulated copper wire
I o c c pipette calibrated t o deliver
-
. .
,

I o c c pipette ca librated to contain

-
. .
,

bottle wi th fi ft ie t h n ormal potassium chloride

-

b ottle with COz free distil led water-

b ottle wi th six tee n th molar solution of acetic b e n zoic

-
, ,

succi nic or other weak acid

1 small b ottle o f mercury

F ig 2 2 illustrates the ma nn er of setting up an d co nn ecti n g

.

the apparatus Th e co n ductivit y cell with its platin um elec

.

tr o des well c o ated with plati n um black is clamped to the thermo

stat in such a wa y that it is immersed up t o w ithin 1 in ch
of the top It is co nn ected in the right arm Of the bridge a n d
.

the k n own resistance in the left arm Th e induction coil is .

co n n ected across the e n ds of the bridge a nd the telephon e from

between the known resistan ce a n d the co n ductivit y cell to the ,

po in t of con tact on the bridge wire With this scheme of W I rI n g .

,

the resistance (x) of the solution in the cell is gi ve n b y the e x

R -b
p r e s s 1 0n x an d the O bser v ed c o nduc t I V I t y c =
a

M e th o d of P r o c e d ure

It is importan t that the position of the electrodes be not

altered durin g the course of the e xp e rnn e n t ; n o r must the plati
1 44 LABORA TORY MANUAL OF P HYS I CAL C HEM I STRY

n um b lack surfaces of the electrodes b e touched S O as t o c han ge

their Character in any way .

P our out a ny li q uid which may be in the cell a n d rin se it

‘

v l
together wi t h t h e electrodes thr ee times with fift ie t h normal
,
-

Co nd u c t
ti i y Ce in

Re s i st a nce Bo x

I dun c t i l
on Co i

FI G . 22 .

KC"soluti o n s ing a few c c at a time Th e electrodes

,
u . . .

b est rin sed b y ge n tl y m ovin g them up and

few times .

After th o rough w ashi ng i n tr od uce 1 0 c c of the fiftieth

,
. .
Cal c ul ati o ns

1 . C alculate t h e cell cons tant .

2 . Compute the co n ductance specific c o nd ric t anc e

,

e q uivale n t co n ductan ce for each dilution o f acid .

3 . F rom T a b le 1 0 obtai n t h e value of the equivalent

d u c t a n c e at i n fin ite dil utio n of the acid used and then calculate
the degree Of io n izatio n at each co n ce n tration .

’
4 C alculate t h e constant o f O stwald s dilut io n l aw f o r
.

each dilutio n .

5 . P lot spec ific and e q uivale n t co n ductances also t h e degrees ,

O f io n izatio n agai nst volumes as a b scissae .

6 Ta b ulate the values foun d in the following ta b le

.

M/I 6 M /3 2 M / O4 M / 1 28 M / 25 6 M /5 I 2

v
Ob s . d u c ta nc e
co n

S pec c o nd u c t a nc e
.

Equ i c nd u c ta nc e
. o

Degree f io niz O .

I niza t i n c o ns t
o o .
150 LABORATORY MANUAL OF PHYS I CAL CHEM I STRY

Appar atu s an d Che mi cals re quir e d

tra nsport n um b er ce l l with S ilver electr odes
I

I copper coulometer

I amm eter ( 1 ampere graduated in h un dre d t hs of

0 —
,

amperes)
I kni fe switch

I t h irt y two volt b atter y -

or direct cur rent source ,

O f greater pote n tial

l

t
- adjusta b le resistance (maximum resistance 200 Ohms )
o
r iro n sta nds
o
t clamps
p- screw co nn ectors
o
o feet of fle xi b le insulated copper wire
H b urette

H b urette holder

N 2 50 c c stoppered E rlenme yer flask s mark ed A

-
. .
,

a nd M
N 2 50 - c c E rle nmeyer flas ks
. .

H p air of cruci b le tongs

H 2 5 c c pipette
-
. .

H 5 0 c-
c graduated
. cyli
. n der
H bottle co n tain i ng copper coul ometer so l uti o n ( 1 50
grams of crystallized copper sulphate Cu S OI 5H g O
dissolved in a mixture of 1 000 c c of distilled . .

water 2 8 c c of H Q S O4 spec ific gravi t y

,
. .
,

a nd 60 c c of ethyl alcoh o l ) . .

sto c k b ottle co n taining s i l ver ni trate s ol utio n ap ,

pro ximate ly grams per liter

sto c k b ottle contain ing standar d KCNS soluti on
( 1 c c b ein g equi valent t o
. . gram of S ilver)
1 00 c c -
bottle contai ning a saturated soluti o n of
. .

n itric acid h as been added to gi v e the so l ut i on

y sis)

b ottle of alcoh o l
 TRANSPORT N UM B ER S 15 1

Th e apparatus is S hown (part ly sc hemat i cal l y ) in F ig 2 3 . .

A three compartme n t cell as gi v en in the s k etch is prefera b le

-

Kn fe i i Sw tc h
mme t e r

for the use of b egi nners as it o ffers less Opportu nity

,

introduction Of errors in d rawm g Off the contents Of the

compartme n ts at the e nd Of
the run A sim ple and e ffi cie n t
.

copper coulometer ma y be
made from a small cr y stal
liz in g dish ab o ut 2 inches i n
diameter and 2 s q uare S heets
,
FI G . 24
.

b y brass spring clips attached t o a hardwoo d electrode

152 LABORATORY M ANUAL OF P HYS I CAL C H EM I STRY

construction provides a con veni en t me ans of holdi ng the

electrodes and does awa y with the n ecessity of termi n als soldered
to the copper sheets With the three compartme n t cell a .
-

pote n tial of 3 2 volts is re q uired to fur nish the necessary curren t .

M eth o d o f P ro c e d ur e
Wash the coulometer cathode with distilled water then with ,

alcohol G rasp it with the cruci b le to ngs and ignite the alcohol
.
,

adheri ng to it Th e cathod e will b e warmed suffi cie n tl y by

.

the b urn ing alcohol to dr y it com pletel y When it is cool .

,

weigh it accurately to a te n th of a milligram .

After weighi ng the cathode clea n a nd dry the two stoppered ,

flasks marked A and M a nd weigh the o ne marked A to

, ,
gm .

Whil e the first stude n t is carryi ng out the operatio n s directed

a b ove the seco nd should clea n a nd dry the cell fill it with stock
, ,

silver nitrate solutio n and assem b le the apparatus Ob servi n g

, ,

care that the ele c trical co nn ectio n s are made as per the diagram .

Nearly fil l the coulometer with coulometer s o lutio n and ,

adjust R to give it s ma ximum resistance .

Close the switch n oting the tim e a nd adjust the resistan ce

, ,

to give a cur re n t of b etwee n a nd ampere Th e .

duratio n of passage of curre nt should b e two hours Duri ng .

this tim e the stre ngth O f the c urre n t S houl d be held constan t
,
.

At t h e co nclusio n of the electrolysis i n terrupt the curre n t , ,

n oti n g th e time carefull y close,

the pin ch —
cocks and with ,

draw the co n te n ts o f the a n od e compartme n t into stoppe red

E rle nmeyer marked A rin sing the compartme n t and the anode
,

with a sma ll amoun t of the origin al solution from the AgN03

i
sto ck bottle O pe n th e pi nch cock nex t to th e a n ode compart ~
.

mer t a nd withdraw the conte n ts of the middle compartme n t

,

i n to the flask marked M b ut do no t rinse this compartme n t ,

-

R emove the cathode from the coulometer rinse it with ,

water the n alcohol a nd dry and weigh as before

, ,
.

Weigh flask A with it s co n ten t s to ,

gm ,
.

Whi le the fir st stude n t is weighing the flask an d cathode ,

the seco nd shoul d determine the concentrations of silver i n the

AgNOs solutio n in the stock b ottle and in th e solution in flask ,

M b y titratio n with stan dard KCN S as follows :

, ,
 1 .F rom the weight of copper deposited in the coulometer .

calculate the weight Of silver dissolved from the an ode .

2 .F rom the total weight an d the an alysis of the anode

, ,

+
solution calculate the amount of Ag actuall y
,
in the
anode compartment assumin g t hat the densit y of the
,

solutio n is uni ty.

3 .F rom the analysis of the stoc k soluti o n ca l culate the

+
ua n tity of A g origi n ally present in the a n o l y te assumi n g
q ,

as b efore that its de n sity is u nity ;

4 F rom t h e data o b tain ed in I
. 2
,
and 3 calculate the
, ,

transfere n ce num bers of the two ions .

 E XP E RIM E NT 23

HY D R O G E N I ON CO NCE NTRAT I O N
E L E CTRO M E TR I C TI TRATI O N

Obj ect
TO measure hydroge n io n co n ce n tratio n electrometrically ,

to employ these measur eme n ts in the titration of acids and

b ase s a n d to Ob serve the poin t of color cha nge of some indicators
, .

Referenc e s
Te xt b o o ks

L i n col n XXXVII E lectromotive F orce p

, , ,
.
540
M illard X VI E lectrochemistry p 3 9 1
, , ,
.

S pec ia l Te xts

Clark , Determinatio n of H ydr o ge n I o ns wh i ch ,

S
ta ins a f ai rly complete b i b liography up to 1 9 20 .

L each Win to n F ood I nspectio n a nd Analysis p 1 0 2 1

-
, ,
. .

L ewis A ystem of P hysical Chemistr y Vol

,
pp
,
. .

26 1
—
2 52 .

1 Wes ton standard cell

1

I
15 8 LABORATORY MANUAL OF P HYS I CAL CHEM I ST RY

device calomel electr ode hydrogen electr ode and b urettes is

, ,

not shown Th e Kipp ge n erator or preferab ly the hydroge n

.

tank ) and the wash b ottles are also left out I n case a ge nerator .

is used arse ni c free zinc and acid sh o uld b e employed

,
-
.

FI G . 25 .

Me th o d of P r o c e d ure
carr ying out electr omotive force
In
a pote n tiometer it is n ecessary fir st

E . M F of the standard cadm ium cell is

. . v olt at 20
°
 G
H Y D RO EN I ON CONCENTRATI ON 159

°
( t emperature coe ffi cie n t between 1 5 and 2 5 equa l s
per degree) If therefore the sliding contact b e set at
.
,

cm ( for a ro o m temperature of
. and the curren t in the poten
t io m e t e r circuit so regulated that the drop i n pote n tial alo n g
the w i re between M and P is equal to the p o te n tial of the stan d
ard cell then each cen t imeter on the pote n tiometer scale from
,

M t o a n y point p will correspond to a potential of v olt .

I n o rder to regulate the curre n t i n the p o te n ti o meter circuit ,

thr o w switch D i n to position a thereb y mak i n g c o nnection ,

with the standard cell C lose S and set P at the proper readin g .

the n close k ey K for an instant b y a light tap and n o te

S
which way the galvan ometer needle is deflected D O no t allow .

an appreciable curre n t to flow through the standard cel l or its

E M F wi ll be altered . hift c o ntact poi n t X and agai n close
.

the galvan o meter ke y K A few Observatio n s Of this character .

wil l suffi ce to adjust X until no deflection is n oted when K is

closed Wh en this is the case the drop al o n g M P is e q ual t o
.
,

the E M F o f the standard cell

. H .

H avi n g properl y adjusted the current o f the pote n tiometer

circuit pr o ceed with the measureme n t of the electromotive
force set up w
,

he n the S ide arm of the calomel electrode and the

hydrogen electrode are immersed in a solution co n tai ni n g hydro
g e n io n s .

S
A Titr ati o n
. of NaOH with H Cl .

i
lip the woode n b lock from b en eath the titratio n b eaker ,

empty the latter a n d r inse with distilled water takin g care to ,

rin se the electrodes an d stirr n g device also .

R eplace the beaker add 2 5 c c Of distilled water pipette

.

,
. .
,

2 5 c c of tenth n o rmal N a OH into it a n d add two drops of methyl

. .

oran ge I n rin sin g the beaker an d the electrodes wor k rapidl y

.
, ,

in order that the hydrogen electrode ma y n o t b e exposed to the

air lo n ger than is a b solutely n ecessar y F il l o n e b urette with .

te n th n ormal H Cl .

S tart the stirrin g de v ice an d pass a b risk stream of hydrogen

through the electrode 1
.

See C lark l c p 3 3 1
,
. .
, . 1 .
1 60 LAB ORATORY M ANUAL OF PHYS I CAL CHEM I STRY

Throwswi tch D in to po siti on b thereby conn ecting the ,

hydroge n electrode with the slidin g contact P Depress K .

for an in stant and adjust the position of P until n o deflectio n

is noted o n the galvan ometer when the ke y is closed Avoid .

passin g a large curre n t through the gas chain or i t wil l become

p olarized .

R ecord the position of P tak in g cons ecutive half minute ,

-

readi n gs until a co n sta n t value is obtain ed .

Add 5 c c of H Cl from the b ur ette an d o b ta in a new value

. . .

C ontin ue the additio n of acid measur ing po te n tials after addin g ,

1 0, 1 5, 1 8, 21 ,
23 , 24 ,

2 7, 28 ,cc 29 and 30 . . M ake note of first an d seco nd

color change of the i ndicator .

B . Titr ati o n o f NH 4 OH with H Cl .

C heck the adjustm e n t of the po te n tiometer curre n t b y

throwing t h e s witch D in to position a settin g t h e mova b le ,

co ntact at and if necessary readjus ting the position of the

co n tact X as previousl y directed .

After r in sin g the titratio n vesse l e l ectr od es an d stirrer , ,

place 2 5 c c of distilled water a nd 2 5 c c accurately measured

. . . .
, ,

of te n th n ormal amm onia solutio n in the beak er Ad d two drops .

of cochin eal in dicator .

P roceed as un der A rec ordin g s imul ta n eousl y volumes of ,

acid added and pote n tiometer readings Note the exact poi n t
,
.

at which the in d icator chan ges .

C . Titr ation of Ac e ti c Ac i d with Na OH .

C heck the po te n tiometer curre n t replace the solution in ,

the beak er wi t h 2 5 c c of dis till ed water and 2 5 c c of acetic

. . . .

After
adding two drops of phenolph t halein add in t h is case ,

fr o m the second b urette te n th normal N aOH ,

.

R ecord volumes and po te n tiometer read ings as before and

note the v olume when the first permanent fain t pink appears
in the beak er .
1 62 LABORATORY MANUAL OF PHYS I C AL CHEM I STRY

M ultiply the pote n ti o meter readin gs b y

1 . 2 in o rder t o
obtain the E M F . . .

C alculate the value of pH in each case from the equat i on

2 .

for the cell : "

calomel electr ode ( co n taining n ormal KCl) solu
tio n h ydrogen electrode "

E . M . F .
pH

or appro xim ate the value of pH from the pH

,
curve
( F ig .

3 P lot the.n um b er of c c of reagent added aga in st H

p fo r . .

each titratio n made noting the neutral po int ( pH = 7) and also

,

the point at which the i ndicator changed color

4 If the latter did n o t change at the
. neutra l point
e xplain the discrepancy .

ll i l l lv l
l l l ll l
G rap h s sh o wing re at on b e t wee n o t ag e of gas
t r a t io n (p H) .

A fo r
. a N m a K C"c a m
or tr d o e e ec o e.

F
B . fo r a N m a ca m
or ct d o e e e ro e .

C fo r
. a sat at d KC"c a om l ec t ro d
ur e e e e .

IG . 26 .
 S
I E NT 24
E XP E RIIV

E L E C TR O M O T IV E FOR CE M E ASUR E M E NT : CON

C E N TRA T I O N C E LLS
.

Obj e c t
To meas ure the electromotive force of co n ce n tratio n cells ,

to determin e t h e co n ce n tratio n o f a AgN03 solutio n an d to -

,

measure the s olu b ility of AgCl .

Te xt b oo ks

B igelow XXIX Th e I n te nsity F actor p 4 7 6 , ,

.

G etm an XVII E le c tromotive F orce p

, , ,
.

Jo nes VII E lectrochemistry p 44 2

, , ,
.

L in coln XXXVI I E lectromotive F orce p 5 2 6

, , ,
.

M illard XVI E l e ctrochemistry p 3 7 1

, , ,
.

M orga n IX E lectrochemistry p 4 2 2
, , ,
.

S e nter XIV E lectromotive F orce p 3 6 7

, , ,
.

Wa lker XXX E lectromotive F orce p 3 63

, , ,
.

Wash b urn X VI C o n duction of E lectricity p 20 1

, , ,
.

E well , I n tr oducti on p 5 7 , .

F i n dla y XI M eas of
, ,
. p . 213

F ir th XV M eas of
,
p 1 07 ,
. .

Getman X I E lectromotive F o rce p

, , ,
. 1 83

P ring ,
Pt . I ,
E le c t ro c h e m .
, p . 81
1 66 P HY S I CAL CH E M I STRY

FI G . 27 .

8 t 'd C e l l
.
 E L ECTRO M OT IV E F ORCE M EA S URE M ENTS 16 7

M e th o d o f P roce d ure
Cl ean a nd dr y the half cell e l emen ts a n d the 50 c c beak er -
,
-
. . .

Place a b out 4 0 c c of n ormal KN03 m the latter

. . .

H old the fin ger o v er the tip o f the half cell marked N/ 1 _

-
,

a n d pour su fli c ie n t n o rmal AgN03 i n t o the v essel to fi l l it t o

a poin t just below the upper side arm Pl ace the sil v er elec -
.

trode 1 in positio n a n d close the sid e arm then rem ov e the

,
-
,

finger from the tip M ake sure that the elemen t does n o t l eak
. .

F ill half cell marked N 1 0 with tenth normal AgNO3 in

- -

lik e mann er .

P lace the more conce n trated solution in position L and ,

the more dilute in R ( F ig M ake all electrical connectio n s

S
.
,

as per the diagram ( F ig .

et dials A an d B o n the poten tiometer to c o rresp o nd t o

the poten tial of the standard cell se e page 1 58 C lose switch -

,
.

S and t hr ow double p o le switch X to co nn ect with the standard

,
-

cell .

C lose K f o r an in stan t an d ob ser v e the deflect io n o f the ,

galvanometer B y suitabl y adjusti g the resistan ce R an d

. n 2

tapping K the curren t in the poten tiometer circuit ma y b e

,
,

adjusted u ntil the gal v anometer gives n o deflection when K

is closed .

Th e p o tenti o meter is n o w in co n dition to read electr o motive

force directl y fr o m its scale .

Tu rn di al B unti l it reads zer o and throw switch X t o make ,

connecti on wi th the E M F to b e measured . . . .

Tap K an d n o te the deflection of the galvan o meter

,
Adjust .

di al A until i ts position c o rresponds t o an E M F o n e step . .

l ower than the p o tential of the concent ratio n ce ll then adjust ,

dia l B unti l a balance is secured

d
.

1
rd er th at th e silver el ec tro d e s ma y po ss e ss a u ni fo rm po ten ti a l t h ey
In o ,

s ho ul b e k ept s ho rt c ir c ui te d in a s o l ut i o n o f N / 0 AgNO when no t in u s e

“ -
"
1 a .

I n th e a d" u s tabl e re sis ta nc e s ho w n di al is for r ug h fo r appro xim ate and , 1 o ,

2 ,

3 fo r ac c urate a d" u s tmen t Turn 2 an d 3 c o un ter c loc k w is e a s far a s t h e y w ill -

, .

go a nd a d "
, u s t I un t il t h e c urre n t in t h e po ten t i o meter c i r c u i t i s slig ht ly g reater
th an th e pro per s treng th fo r b a l anc e ; then dim i ni s h th e c urren t by turni ng in 2

a c l k wis e direc tio n and finally a d"

oc ,u s t i t ac c urately by means o f di al 3 .
1 68 LABORATORY MANU AL OF PHYS I CAL CHEM I STRY
.

R ecord the electromotive f o rce of t he co n centratio n ce ll

(Ag N/ r AgN03 : N/ r KN 03 : N/ 1 0 AgNOa Ag)

F ill half cell marked N/ I OO with hundredth no rmal AgNOa

- -
,

place it in po sitio n R transferr ing the te n th n ormal solution to

,
-

position L Co nn ect X with the standard cell a nd check the

.
,

value of the pote n tiometer curre n t .

R eturn X to the o t her positio n measure a nd record the ,

pote n tial of the co nce n tration cell :

( Ag N/ 1 0 AgN03 N/ 1 KN03 N/ I O0 AgN03 Ag)

R eplace the hu ndred th normal solution with a solutio n of

-

u nk n own stre ng t h in eleme n t marked N/x check the pote n t

, ,

t io m e t e r cu rre n t a nd me a sure a nd record the E M F of the

,
. .

cell :

( Ag N/ r o AgN03 N/ 1 KN03 N/x AgN03 Ag)

R eplace the solutio n o f unkn ow n stre n gth with cell marked

Ag C l co n tain in g a solutio n made up as foll ows
,

F il l the cell with N 1 0 KC " an d add o ne or two drops of ,

N/ 1 AgN03 in order to produce a saturated solutio n o f Ag Cl

, ,

in the cell P lace the N/ 1 00 AgN03 cell in positio n L

. .

C heck the po te n tiometer and measure a nd record the ,

E M F of t h e cell : ( Ag N/ I OO AgN03 : N/ 1 KN O3 : satu

. . .

rated AgCl in N/ 1 0 KCl : Ag) .

Disco nn ect b o th wires from the stand ar d cell an d open ,

switches S an d X .

Remove the solutio ns from the ha lf ce ll elements pour -

,

them in to the sil ver residue bottle and rin se the ce lls wi t h d is ,

tilled water Open all coc ks and invert the cells in their sup
.
,

po rts so th at the y will drain

,
.

Wash the electr odes conn e ct them all together by means

,

of a piece of copper wire and leave them in a tenth norma l ,

-

AgN03 soluti o n contained in the 1 00 c c beak er

,
-
. . .
1 74 LABOR ATORY MANUAL OF PHYS I CAL C H E MI STRY

At H igh Te mper at ur es

IN DEX or WATE R Pox

 TABLES 175

D E N srr rE s ( d4)

ME R C or V AR I U I UI
O S L Q DS

A . U RY ( R e gn au l t B r c h )
-
o

B . W ATE R ( T h i e s en Sc h eel Mare k )

, ,

'
C . I
N TR OB EN ZENE (v an Klo o s ter )

D . C H LOROB EN Z ENE ( J ae g er)

. I . 05 1

E . B ro m o b e n e n e
z ( J ae g er )

F . C ar bo n tetrac h lo r id e (J aeger )
O

70
B P
. .
76
 B o ru x c ~1>o mr C ON STA N TS ( per 1 00 G ram s o f v
So l ent )

S u bs t a n e
c

F ro m Rosa no fl
'

an d Du nph y , J . Am . C hem . 1 41 5
17 8 LABORATORY MAN UAL OF P HYS I CAL C HE MI STRY

TABLE 9

( c o n ta i ni ng G ram s pe Li ter) at
r

EQ UI N U NCE
V ALE T C OND C TA S AT
TABLE
I NP 1N 1TE
10

D IUIN
L T O or WE A K A CI DS at 25
°

o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

o o o o o o o o o o o o o o o o

TR A N S P O R T N UTABLE
MB E RS
11

OP C ATI ONs AT 1 8
°

M Ax m w C UC CE
I ONI C OND TAN S AT 1 8
°
 TA BLES 1 79

R ED T OUC I N or
TABLE
B AR OM EE E I
T
12

R R AD N G S
When th e h e ight o f the mer c ury c lumn h a s b ee n mea s ure d w i th a gl a ss o r a
o
To 0
°

b rass sc al e the l eng th o f wh i c h is c o rrec t at

,
the merc ury a nd the sc a l e b e i n g
at t the o bs erve d he ight is re du c e d t o 0 by su bt acting the va l ue giv en in the
°
,
°
r

G C C
ta bl e c o rre s po ndi ng t o the temperature and he ig ht .

LA S S S AL E ( B u ns e n) B R A SS S A LE ( D e lc ro s)
.

e
r

B aro meter R ea di ng in mm . t
u B aro meter R ea ding in mm .

a
r
e
p

\ °
m
e
q00 QQ0 8
T A0 (
A0 7 60 7 70 7 80
1 80 LA BORATORY M AN UAL O F P HYS I C AL C HEM I STRY

U C ITABLE 13
F O R P LA E L OGA R TH MS
 TABLE 14

0 0 0 0 0 0 0

C bal t
o

Hyd r ge n
o