Applied CutnZ~sis,14(1985)15-21

Elsevier Science Publishers B.V., Amsterdam

POTENTIOMETRIC
SITES

METHOD

IN COLORED

Ruby CID and

Facultad

FOR DETERMINING

in The Netherlands

THE NUMBER

AND RELATIVE

STRENGTH

OF ACID

CATALYSTS

Gina

PECCHI

de Ciencias,

(Received

15
- Printed

Universidad

26 September

de Concepci&,

1983, accepted

Casilla

'21 September

3-C, Concepcibn,

Chile.

1984)

ABSTRACT
A potentiometric
method was used to determine the number of acid centers and
their relative strengths in colored catalysts. The validity of the results was
established by using measured white solids by the Benesi method and the proposed
method.

INTRODUCTION
The Benesi method
sites

in a solid

solids,

is often

[I]. Unfortunately,

especially
oxides

developed

which

interpret

the data obtained

The physical

with catalytic

properties

has been briefly

reported

system

is titrated

The electrode
electrode

and strength

is difficult

For these

solids,

to apply
which

[2,3], a potentiometric
by Goldstein

of acid
to coloured

include
method

simple
was

[4]. A new criterion

to

is also suggested.

consists

of a solid dispersed

with a solution

potential

the number

this method

if they are weak acids.

and mixed

which

used to measure

variation

of an amine

in a nonaqueous

solvent,

in the same nonaqueous

solvent.

is a function

of the environment

in which

the

is immersed.

MATERIALS
The reagents
acidity

Te02,

used were pure n-butylamine

was determined

Fe2(Mo04)3,

and Fe2(Te03)3
A type-Y

Fe2(Mo04)3

+ 5% MoO3,

zeolite

used had a grain

digital

for the following

+ 5% Te02,

prepared

and pure

solids:
Te2M007,

according

Te2Mo07

with

+ 5% Fe203,
already

The surface
MoO3,

FeE03,

Fe2(Te0313,

C51.

described

71% of NH; [6]. The solids

106 and 150 urn, calcined

pH meter with a combination

Si02-A1203,

to a technique

has also been used, exchanged

size between

acetonitrile.

AlE03,

glass and Ag/AgCl

at 500C for 4 h. A Beckman

electrode

was used.

METHOD
A small quantity
mass of solid,

of 0.1 N n-butylamine

and agitated
-1

same base at 0.05 ml min

0166-9834/85/$03.30

in

for 3 h. Later,

. The electrode

0 1985

Elsevier

Science

acetonitrile
the suspension

potential

Publishers

B.V.

was added

to a known

was titrated

variation

with the

was registered

on

16

H(71)-NaY

meq.
g.cat.

E(mv)

320

240

160

gx 103

H(71)-NaY

0.

-80.

-160 _

I-

320

FIGURE

1 Potentiometric

FIGURE

titration,

The acid strength

160

ElmVl

NH4(71)NaY.

Benesi method

distribution,

and potentiometric

method,

for NH4(71)NaY.

a Beckman

digital

pH meter.

to reach equilibrium
of the electrode
We tested
solvent

such as

DISCUSSION

depends

potential

benzene,

of butylamine

acetonitrile

of the solid

of base used

used. The reproducibility

mV.

acetonitrile

to eliminate

as a solvent.

the problem

We chose

of irreversible

a polar

adsorption

[7].

AND RESULTS

(a) the standard

electrode

electrode

the measured

if the electrodes

electrode

potential

may arise

from

used were of glass and calomel

[S],

could be due to:

junction

(c) the difference

method,

For example,

potential

(b) the liquid

calomel

and

from an inert solvent

sources.

the measured

on the acidity

curve was 3

isooctane

In this potentiometric
several

The mass of the solid and the quantity

potential

potential

of the reference

between

and the dispersion

in potential

across

the aqueous
in

electrode
KC1 solution

acetonitrile

the glass membrane

outside

inside the
the electrode

separating

the dispersion

17

SiOZ-A1203

t-4 t

1.6

SiOZ -A$03

LO

21)

FIGURE

method.

in

The acid strength

acetonitrile

(d) the potential

and the aqueous

Gv,

-80

distribution

of the sensing

80

!60

metric

of Si02-A1203,

buffer

electrode

solution
within

Benesi method

inside

and potentio-

the electrode,

the glass electrode,

and

the Ag-AgCl

interface
Since

(a) and

does not appear

(d) remain
to change

that the electrode

imposed

unchanged

during

an experiment,

appreciably

during

a titration.

potential

on the outside

is determined

primarily

of the glass electrode

effect

(b), if present,

Therefore,

it appears

by the acid environment

membrane

by immersion

in the acid

particles.
To prove the validity
three white
methods,
values

solids was determined:

the Benesi method

of total

measured

of this potentiometric

through

acidity

method,

Si02-Al203

A1203,

and the potentiometric

could

be obtained.

the surface

acidity

and- NH4(71)NaY

by both

method

This NH4(71)NaY

in order
which

of

to see if equal
has already

been

the Benesi method, gave potentiometrically

(Figure 1) the same
-1
cat [9]. In order to obtain an acid strength
2.9 meq g

value of total acidity,

distribution
compared

as obtained

with Chessick

by the Benesi method,

and Zettlemoyer's

method

the potentiometric
[IO]. They noted

method

was

that the potentio-

18

meq/g.caf

102

<

30

Te 02

MOOg

20

(I
I

II)

CI

0.0
20

60

100

-20

-60

-100

L
-110

EImVl

FIGURE

4a)

FIGURE 4b)
Te-0 system.

The titration

curves

The distribution

for the simple oxides

of acid strength

of the Mo-Fe-Te-0

for the simple

oxides

system.

of the Mo-Fe-

19
metric

curve was similar

butylamine

to the differential

of n-

on attapulgite.

Following

a procedure

of argon on rutile,
function,

used by Drain and Morrison

Chessick

and Zettlemoyer

g(E). The heat of adsorption

n-butylamine

vs. heat of adsorption

The potentiometric

titration

does not mean that there

The acid strength
the Benesi method
where

heat curve of adsorption

with

potentiometric

cordance

between

fication

1121,

is calculated

can be handled

is an equivalence

Hammett

titration

a site energy

distribution

from the slope of the adsorbed

(nHd) curve as:

curve

distribution

[Ii] for heat of adsorption

calculated

of thermodynamic

was calculated

indicators.
was used.

although

it

values.

for the zeolite

NH4(71)NaV,

This is shown in Figures

It can be observed

them and, based on the Hirschler

it can be concluded

in the same way,

that there

and Schneider

using

2a and 2b
is a con-

acid sites classi-

that there are sites of moderate

acidity

in the

solid.
The acid distribution
is shown

in Figure

3. In our opinion

of the potentiometric
of the Si02-A1203
method.

method

sample

These sites

concordance,

of Si02-A1203

seem to be undetected

can be detected

sites

solids.

Te system

is shown

acidity

obtained

by P. Ratnasamy

and Hammett

available,

Te02, as the promoter

shown

in Figure

the validity

the strong

though

there

has strong

to the determination
for the simple

sites

is not

or intermediate

4b.

mistake,

The latter

although

be noted from the millivolt

can be related

method

that pure MoO3, obtained

acidity.

The Te02

of mixed oxides,

similarly

range.

with
with

to the
shows

the role of destroying

of each of the oxides

the inflection

but

In the bibliography

is

near 20 mV may be an

the same type of curve was obtained

in acid strength

agrees

by titration

is the oxide which

is given

of acid strength

In the case of Mo03,

acidity

of the Mo-Fe-

the Moo3 has only a few acid sites,

using the potentiometric

The distribution

of the

oxides

that not only the value of

range.

of acid sites and these are very weak.

In Figure 4 the great difference

very

methods

by the potentiometric

et al. [13]. They determined

strong

density

experimental

Thus,

indicators

showed

the lowest

acid sites.

was applied

curve obtained

of the solid.

one used in this work,

surface

supports

although

by the Benesi method,

but also the millivolt

ones. The result

n-butylamine

clearly

4a. It can be observed

in Figure

to the acid strength

strong

obtained

if the silica-alumina

method

The titration

found changes,

the one obtained

and Benesi

[7].

Then the potentiometric

of colored

the concordance

used in this investigation,

in the bibliography,

acid strength

by the potentiometric

between

three times.

the three oxides

can

Te02 shows only one type of acid site and

weak, but Fe203 shows clearlytwo types of acid sites,very weak and weak,

20

-20.

-20

2
:

i
-60

0
Q
t

0
-60
08

OL

12
mrq/g

FIGURE

The titration

curves

for oxides

16
cat I to2

and promoted

oxides

of the Mo-Fe-Te-0

system.

and Moo3 seems to show only one type of site, not very strong.
As a criterion
initial

electrode

for interpreting
potential

sites, and the range

the total number
site density

clearly

N(millieq

seen that an addition

of thesites

it is suggested

acid strength

solid) where

Knowing

hand, by this method

with the same catalyst

acid sites of Fe2(Mo04)3,

varies.

5X FezOX are shown.

acid sites which

the plateau

the specific

the acidity

of Te02

that the

of the surface
is reached

area of each solid,

It can be observed

catalyst

in Figure

in the bibliography

either

acidities

indicates
acid

in a-TepMo07

strong

it is
of

[141, but the strength

and a-Te2Mo07

of Fe203 generated

strong

or in Fe203.

t 5% Mo03,

acid sites,

can be

5, where

the total number

of a-Te2M00,

that the addition

and Fe2(Te03)3

of Moo3 does not create

of a given

is shown

(5%) does not decrease

as suggested

are not present

This

promoted.

In this same figure,

In the case of Fe2(Te03)3

addition

base/g

of acid sites.

obtained,

the maximum

can be calculated.

On the other
compared

the results

indicates

it can be observed

although

that the

the pure Moo3 shows

then. The data shown

oxides

It is apparent
number

in Figure

in the total oxidation

5 agree with the activity

of propylene

that the potentiometric

of these promoted

mixed

[15].
method

of acid sites and their distribution,

enables

determination

of the total

The color of the catalytic

solids

is

not a limitation.

ACKNOWLEDGEMENTS
This work was supported

by Direcci&

de Investigaci;n,

Universidad

de Concepci6n,

Chile,

REFERENCES
1
2
3
4
5

IO
11
12
13

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