Verslag behorende bij het processchema: Nitrobenzeen uit benzeen en salpeterzuur

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Solubility af nitrobenzene I in waste aciel NO.l Aciel contains O.2%HNOI

Ij)

NORat.2 io NS+rai~t .B. waste 1H25O .. :2 Time 30 min.

~

Temp. 110 eleg.F.

~N

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1

No.l Wosh water anel H.SO..

I

NO.2 " " • _NaHC03 Time 30 min. TemR.1I0 deQ.'

-,No.2 Ratio 1:2

I I I

NO.l r

I· I

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2 3 4 5 6 7 8 9 10

Per Cent H2SO .. or PerCent NaHC03

NO.t·

Ho 1 Solubility of nitrobenzene

in water 1

Time of separation 30 min

I

Ko.2 Solubility of nitrobenzene

I

in WOIste

r·

acid SO

-4 74.5%

I

W.A. H N03 0.&

H20 25.0

Time 30min. Ratio N.B.-WA 1:2

NO.2 .

ff

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-40 50 60 70 80 90 100 110 120 130 140 150 160 110 180

Temperature ef Separatien, Oeg.'

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explosln. for

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_~

IDGDU-lcictdt~of:

' . ", ': " 1 dy •• cmd '

aynthetic orqcmlc:

ehemlcala.

. . ,

th.

eh_cal

qql-,

_r

.

h~ &equ.D~

.

1188

for thermal data

In ca1culatlDq heat

balancee

,è:DI.d-lIlzDIlar operat1nc; facton.

Th.

enthalpy

cbart.

pr8Na"

In

tbI8

'

pciper

mak ..

these

thermal propertl . .

of

lDlxec:ld:c:Ida

~

readtly

avallabl. for praCtical UA In calcu1at1ona of

thk

ldD~tor

..

M

,lXED ACID, a mixture of

sul-phuric acid" Ilitric acid, and

water,' is commonly 1l8edas the

ni-~ating agent' in commercial nitratiori

reactions. These nitration reactions

Î.re

'the blUliS of our expiosiyes

indus-tO' ,and are ~ important inthe

pro-ilJ19tion .of, d~, dye intennediates

4J)d other industrial organic ehemi-eals. The thennal properties of mixed

acids are' not readily ' available ,as

some of tbe data

are

,

in French änd

~1

'

ot

.

the figuree ; are not giVeJ;l

in engmeeringunlts. The enth~p~

chart presented here makes these

thermál propertiesreadily available

".n~ usable tef heat balance and,

simi-lar

:

ealculatWns.

Con8#fltlCtio"ol Cllarl-Each set of dáta on 'heats of S()lution or dilution

(I, 2, 4, 6, 7,8, 10, 11, 12, 14-) was

recalculated to obtain the relative en-thalpy of one pound of solution at 32

deg, F. referred to each pure

com-ponent at 32 deg. F. The relative enthalpies so. computed were then plotted on.a triangular ternary com-position diagram (Fig. 1) and lines of constant enthalpy were drawn, In drawing these iso·enthalpy lines the data of McDavid (7), of Pretat (11), and of Rhodes anrl Nelson (12) were espeeially relied upon. Lines r~pre senting constant neid ratios were then drawn as indicated, starting at the acid ratio in question along thc

H.SO,-HNO. side ofthe triangle

(0, percent H.O) and extending to the H.O corner. The intersections of these acid ratio lines with thc

iso-" '

enthalpy lines were then used in

plot-ting the ternary enthalphy data upon

a Pseud9 binary hlUlÎ8. (Fig. ,~). .

Tbe reijable experimental data (7,

11, 12),. ~ ~ong themseJves

usually within 3 to 4 Rt.u. per lbo

iJl

ov~l~p~g ~~ andshow no de

-putu,e g~, than7 B.t.u. The

1IR&1plót

agrèe8

lrjih ~e ~ore

reJia.-bIe, data

"

wiihin

'4-lU,u.

1*

lb. of

selutionm: ~~y all

cues.

.

c

U66

of

e.,-The

ordina~

of

,Fig.

" _;"

: ,

I

.,

, ',' '.1

.'

,

2 u 'entbalP1 in'UB;t.u.'per lb. of

101ûtion" ·imd the abseisMiS "p~t

bY

weïght of total acid in the mi1ecl

. ACid aolution!'. Theenthalpy for a

speeiftc

composition is obtained 'bY·

interpolation between the lines 'of

,

indicated

niw acid composition,

being b~on -anhydrous HNO.

+

H.SO" and for the total acid

eoncen-, tration as given along tbe abseiasa.

For e:xample the line of 60

percent

HNO. on this plot represente the

enthalpy at 32 deg. F. of all mixtures .

of water with an acid mixture

contain-ing 60 pazts nitric acid to 40 parta of

sulphllric acid on tbe basis • of

anhydrous acid (HNO.

+

H.SO,).

The enthalpy of a mixed acid

con-taining 30 percent HNO., 20 percmt

,

11.80.,

and

50

percent

litO

as

l'ead

from the charl is

-106

B.t.u., per

lb

:

of SQlution. Thè steps involved· ~

set forth in d~ in Example

4 .

.

The enthalpy values .. read

ffoDi

.

tb!!

ePart

are referred to tbe 8~

state of the pure compontmts ~O ..

u.sO., &Qd

HaO,

eaoh

bavÏDi

zerQ ..

enthalp'y at

32

deg. F.

This

ref~

• See 'blbIlography at end of artlcle. Fiq. 1. r.o-eo..thalpy chárt for mixture. of "ater. au1phurlc and nltrlc aelds.

142--5 - JC.A.Y 194f - CHEMICAL & METALLURGICAL ENGINEERING

(20)

,

~." -f.:~.

,

f ~:

.

if_, .. ,.

, .

.

I~--~~~~~--~--~~~~.~~~~~~~~~~~

eo~pondÏJ)g.

to ~ ~;to~~

'

,'

l*ted on

thé

fine

'

'AB

at. I pobl~ . 'lWÓ"tlifrdi!l the-distancè

lrotD.

:i

~ B, "

i.e. C,with

a

total ácid

:

eonéènt!~~OIl

of 60 perC4lnt. Thè enthalpy·ol"tJûa.

final mixture is read along tb. enthalpy scale as

-94.5

B.t.u. per lb.

,The enthalp.y of -94.5 howeover

, represents for the final concentration a temperature above ~2 deg.

F.

There.. fore the percent HNO~ eannot he read direetly at

tbis

point C •.

Tile

enthalpy of the. final mixtW'e,

at

S2 deg. F. is read from the ehiU't b a

, total aeid concentration of 60 percel and a HNO. in the total' ,anh~

aeid of 70.0 percent &8 -l'M.S; ~e '!lnal enthalpy óf -94.5 is (-9ll)'

+

104.8 ::; 10.3 B.t.u.) 10.3 B.t.u. ~,,,,,.

greater than the enthalpy of theflnal

: ,~ution .at 32, deg~ F. TherefQlf8 ~~a

B.t.1?-. pil' lb.,~ hé reDWlveil:ialtie

'

!niXiAi

óUh8118

t,;o

'

oiiginal

8Ollatlona

if it ia to

he

aoeomplWled

iab ... •

.uy

at 32 deg. F. lf no h_t ia

'l'eDlOved the hal temperature will- he

.' ., ... ,~) .., . '10.3 .... . _ .10.3

~k=>-~~+!.:...:..~

'

,'

.J;.,

,

+-

~

...,.J.--l--.J. ...

~-,j-..:.::....+-+..,....,,+Io.9

3J

dec·

lI'.'+ :-;;-

~. 0iI~

,

. .r.

~

.

~~

.

"; 10 • ..: t:l1$ r •• " • "'{ln .• ;, ; '._ ,i _: _·_'.'_rt_"·_:=-_;_q·~ ,:,; .l ,

_,.

0; !- ..:. ,,' \ '(p , " .. ",

· ttr

". ' •. :;.;' ,:-. ~,,'" . ,H: 1\ .'.~'-'.' , " ..t :'i,,' -IL ' 48.4dic-F. , . , " , ,.;.,10>-,

..

~~(:...;..:....::+--4-

...

~

.,

....,

.

...

.

+-"'-+-~4-~J-I.""

'

.

Plotted on Fig'. 2 -

_l«t

,

t1ië.UJhe

.. '

.

a';t

agaw

'"

'.beeissa

but against differéit~'

ordi-,.,. i, ,.t. ';

,

i

'

nates are' the speciflc heat

dAta

'

for

~""!'_--1~~~_-+Pu==,.~(UtOJ~:L-4;;.\

"

'

::':'

"

-~..!.I2hI-l1~o.

7 al the

eyatem.

Prom thia figure, coritain·

ingbóth 32

deg.

F. ré1ati~,.eath.lpieB

and speciflc heats; the' enthàlpy of any liquid mixture . of, nitti( aéli.d, sulphuric aaid, and water may he readily calculated. by leadiDg the

de-sired relative enthalpy at 32

cIM.

F.

and the speciflc heat from

tbs

ahart

as bas been indicated above.' '

The available data on· heat aapao-ities' (3;

!t

13, 14) 'are all at subetaD-tially 70 deg~ F. or room temperàture.

,·Therefore the heat capacities plQtted

, in Fig. 2 are at 70 deg. F. but may he used over any temperature range until ,data for di1fetent temperatures

. . . ~ äre' á~ailabie. . .. , . '. "

Following are ~hree ,examples

illWl--trating the method of ming Fig.

2-EXAMPLE A

Find tbe relative enthalpy' of " mixed

acid of tbe following ,compoeitioD at

9Odeg.F.:

HN<b 30 pelC6}lt

H,80, 20perceilt HsO 50 peroent

Percent HNO. on anhydro~o~"wa~ ~ree 30 ' ' , .. ~ ... , ....

ba8ià '" - X l00,-60~

~~_-i

';

~

...

L

·

the aIieefaa Pd.. ai' ' . eeilt (1)' tbe

~ ij,NOtUnell -~06 B.t.lIo/lb. .' BOlution' ànd lIP. ~t. 0:= .66 B.t.u./llt,

_u-,,/ tionrF; ,.."

" ... Hto- - -106

+

(9(h'32) (.68) =

-67.7 B.t.u./lb:

(21)

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