Zeolites and their synthesis

Richard M. Barrer, F.R.S.

Physical Chemistry Laboratories, Chemistry Department, Imperial College,

London SW7 2A Y, UK
7eolite synthesis is an area of classical hydrothermal chemistry which has developed to a
stage where generalizations are possible which may be considered coherently. A review is
therefore made of some aspects of zeolitization giving it, firstly, its setting among other
crystal growing procedures and its relation to pH and temperature among other minerals
which can be made hydrothermally. Reactants and reaction variables involved in laboratory
synthesis are described, among the latter notably the mineralizing role of OH-, structure
directing effects of cations and organic bases, the influence of added salts and various
history dependent effects. Finally an account has been given of nucleation and nucleation
kinetics and crystal growth.

INTRODUCTION
There are two good reasons for studying the
chemistry and synthesis of minerals. First is the
understanding of reactions in the lithosphere, often
vast in scale and in the range of the variables,
pressure, temperature and time. The second is
technical and strategic - the search for replacements of scarce and valuable minerals, or for
synthetic and novel substitutes with specific builtin properties. Zeolite synthesis provides a good
illustration of this.
Some early examples of silicate species formed
b y several crystallization procedures are given in
Table 1. This table shows that hydrated minerals
like clay minerals and zeolites can be made only in
hydrothermal systems, i.e. from reactant mixtures

in the presence of substantial amounts of water.

On the other hand anhydrous minerals like felspars
or crystalline silicas can be made by several
methods not necessarily involving water. The
sodalite and cancrinite minerals are an interesting
group in that they may be synthesized with their
open frameworks filled either with water (zeolitic
variety) or by salts such as NaC1, Na2SO4, Na2CO3
and CaSO 4 (felspathoid variety). Various intermediate situations with both water and salts
present can be achieved in hydrothermal systems,
b u t forms bearing only salts can also be made
from melts.
ZEOLITES
Zeolites have been studied by mineralogists for two
and a quarter centuries beginning with the first

T a b l e 1 Some mineral syntheses by f i v e methods

Mineral t y p e

Hydrothermal

C l a y minerals

K a o l i n i t e t-s
Dickite4, s
Beidellite %s
Sericite3, s
Nontronite 4
Montmorillonite3, s

Micas

Muscovite 2

Zeolites

Analcime 6
Mordenite 7
Harmotome 8

Sodalite-nosean
felspathoids

Sodalite ~'~
Cancrinite 1
Nosean 1

Sodatite ~8
Nosean is
H a u y n e ~8
U l t r a m a r i n e t9

C r y s t a l l i n e silicas

Quartz H
Cristobalite 12,~3

Quartz =
C r i s t o b a l i t e 2
T r i d y m i t e 2

Quartz 22

Felspars

A l b i t e 14
Orthoclase~% ~s

A l b i t e 21
Orthoclase 2~

A l b i t e 22
Orthoclase 2:
A n o r t h i t e 2:

0144-2449/81/030130-11 $02.00
1981 IPC Business Press
130

ZEOLITES, 1981, Vol. 1, October

Pyrolytic

Pneumatolytic

Sintering

V a p o u r phase

Phlogopite 16,~7

C r i s t o b a l i t e 2s

A l b i t e :3
A n o r t h i t e 24

Zeolites and their sgnthesis: R. 114.Barrer

Table 2 Intracrystalline pore volumes in selected zeolites (as cm 3
H20 per cm3ofcrystal)
Zeolite
Analcime
Natrolite
Thomsonite
Heuiandite
Stilbite
Phillipsite
Gismondine
Garronite
Mordenite
Ferrierite
Epistilbite
Chabazite
Levynite
Mazzite
Erionite
Faujasite
Paulingite

Intracrystalline porosity
0.18
0.21
0.32
0.35
0.38
0.30
0.47
0.41
0.26
0.26
0.34
0.48
0.42
0.37
0.36
0.53
0.48

member, stilbite, discovered in 1756 z6. However

their spectacular applications in industry have been
developed only in the last 25 years. They are tectosilicates, so that (Si + M ) / O = 1/2, with as many
equivalents of exchangeable cations as there are
g atoms of A1 in the aluminosilicate frameworks.
Because these frameworks are so porous their
interstices hold not only the cations needed to
neutralize the anionic framework charge but also
large amounts of water. Table 2 shows for a
number of zeolites the volumes of water, as liquid,
which can be displaced b y heat and evacuation
from each cm 3 of crystal. Up to 50% of the volume
of each crystal consists of minute pores available to
water and often to many other guest molecules.
Because the zeolites are crystalline the pores are as
regular as the positions of the lattice atoms
forming their walls, and they are of molecular
dimensions only. The open-ness of the anionic
frameworks ensures the easy mobility both of
cations in ion exchanges and of water molecules or
other guest species. Additions and removals of
guest molecules can be fully reversible, and so
zeolites may be excellent sorbents of gases, vapours
and liquids. The molecular dimensions of the intracrystalline channels are such that molecules t o o
large or of the wrong shape cannot enter while
others, smaller or of the right shape, can be
copiously sorbed. Zeolites are therefore termed
molecular sieves, and are indeed like garden sieves
in that certain molecules (small pebbles) pass
easily through the surface meshes of the crystal
lattice and others (large pebbles) do not. Those
that can pass through the surface then permeate
the lattice.
From certain of the molecular sieves acidic
hydrogen forms can be prepared which are the
basis of outstanding catalysts for petroleum
cracking, hydrocracking and other important
reactions. Indeed it is claimed with good reason
that they have revolutionized the catalytic cracking
industry 27. Their successes on a large scale for mole
sieving and selective sorption, as catalysts and in
special ion-exchange uses have made their synthesis

a subject of study in many laboratories in the hope

of discovering new industrial 'winners'.
Synthesis is also stimulated b y the remarkable
structural diversity among the zeolite frameworks.
They represent by far the most numerous group of
tectosilicates (i.e. 3-dimensional networks), with
about 60 different topologies and often a number
of variants of a given topology. Secondly, synthesis
is of interest because many frameworks have been
constructed which have not yet been made or
found in Nature. Indeed the model of zeolite R H O
was built before it was made in the laboratory.
The number of possible novel zeolites is great and
the incentive to find out h o w to make them is
strong. Already a number of the zeolites synthesized
do not appear t O occur naturally, examples of
which are given below:
*Zeolite LTA (Linde A 28)
*Zeolite LTL (Linde L 29) -30
*Zeolite KFI (Zeolite ZK-5 ,
Species P and Q31)
*Zeolite ABW (Li-A(BW) 32)
Zeolite Li-H 32
Zeolite Ba-J 33
Zeolite Ba-K 33
Zeolite Ba-N 34
*Zeolite EAB(TMA-E 3s)
Zeolite N 36 (Z-2137, (Nat, T M A ) - V 3s)
* Zeolite RHO 39
*Zeolite LOS (Losod 4)
Zeolite ZSM-3 41
*Zeolite MFI (ZSM-5 42)
Zeolite ZSM-8 43
Zeolite ZSM-1044
*Zeolite MEL (ZSM-114s)
* Structure determined. The three structural type
letters are those in 'Atlas of Zeolite Structure
Types' by W. M. Meier and D. H. Olson (Structure
Commission of International Zeolite Association)
1978.
ZEOLITIZATION
Stringham 46, basing his arguments primarily on
mineralogical and geological evidence, suggested
the conditions given in Table 3 for occurrence and
formation in Nature of a number of important
minerals, both silicates and non-silicates. The
zeolites are not often formed above 350C and
their synthesis requires highly alkaline solutions.
Smectites such as montmorillonite require less
alkaline conditions and some kandite clay minerals
can form on the acid side and have minimal
amounts of exchange cations. So far as zeolites
and clay minerals are concerned laboratory
experience confirms Stringham's qualitative
arguments. For tectosilicates in general (whether
zeolites, felspars or felspathoids) hydrothermal
growth always requires alkaline conditions. The
main reactants in such systems include those given
in Table 4. The alkali, source of A1, source of Si
and water are mixed in appropriate proportions
are subjected to an elevated temperature, b u t often

ZEOLITES, 1981, VoL 1, October 131

Zeolites and their synthesis: R. M. Barrer

Table 3 Likely relations between pH, temperature and occurrence of some hydrothermally formed minerals 46

600
500

alkalinity increasing

acidity increasing

T(C)

pH = 7
wollastonite
tremolite-actinolite
brucite
adularia

biotite
pyrophyllite
sericite

apatite
400

soo

200

kaolinite
endellite
allophane

pyrophyllite
dickite
~

beidellite
chlorite
hydrobiotite

100

aluiite

gibisite

nontionite

illitesericitetalc
(?)

montmorillonite

calcite
and other
carbonates

zeolites

Table 4 Reactant components used in hydrothermal synthesis of zeolites and other tectosilicates
Sources of charge-compensating cations

Sources of AI

Sources of Si

Alkali metal hydroxides

Alkali earth oxides and hydroxides
Other oxides and hydroxides
Salts (fluorides, other halides, borates,
carbonates, phosphates, sulphates etc.)
Organic bases and NH4OH, especially
quaternary bases
Soluble silicates and aluminates
Mixtures of two or more of the above

Metal aluminates
AI(OH)3, AI2Os, AIO(OH)
AI salts
G lasses
Sediments
Minerals, especially clay minerals,
felspathoids, felspars, and other
zeolites

Silicates
Water glass
Silica sols
Silica gels
Silica glass and other glasses
Silicon esters
Volcanic tufts and sediments
Minerals (clay minerals, felspathoids,
felspars, other zeolites)
Basalts and mineral mixtures
Sediments
Mixtures of two or more of the above

even below 100C: The mixtures may need to be

'ripened' by holding them at or near room
temperature for a period of time before raising to
the crystallization temperature (zeolites X and Y);
and they may during crystallization be stirred
zeolite A), or may be maintained quiescent
zeolites X and Y). Growth times may be in
hours, days, weeks or months according to
temperature and the nature of the reactants.
A favoured reactant mixture has been a hydrous
gel made from alkali, AI(OH)3 freshly prepared,
and silica sol; or from a soluble aluminate, alkali
and silica sol. AI(OH)3 dissolved in alkali, or
soluble aluminate solutions under alkaline conditions, give tetrahedral AI(OH)4 anions. The
species present depend on pH, but under alkaline
conditions AI(OH)4 is dominant. Ionic products
include47:
[H +] [OH-] = 10 -14

[H+p[AI(OII)g] = 10 -23.s [AI 3+]

[H +] [AI(OH) 2+] 10-4.89 [A13+1
:

[H+]2[AI(OH){] = 10-8.s6 [AP ]

Then at pH = 5.87s, AI(OH)~ = A13+ and at p H = 1 0 ,
AI(OH)~+ 1016.sAp+; while at pH = 13, AI(OH)4 =
102S-SA1a .
In soluble silicates, under alkaline conditions
polymeric silicate anions have been found 4s, as
well, in dilute solution in particular, as mononuclear species such as Si(OH)4, SiO(OH); and
SiO~(OH)~-. It is notable that under alkaline
conditiong both the A1 and the Si are in tetra-

132 ZEOLITES, 1981, Vol. 1, October

hedral coordination w.r.t, oxygen, and that it is,

as noted earlier, under alkaline conditions that
tectosilicates, in which this coordination is
preserved, crystallize from hydrous gels and
mixtures. On the other hand under acid, neutral
or mildly alkaline conditions the AI in the kandite
and smectite clay minerals which then crystallize
is mainly in 6-coordination w.r.t, oxygen.
Reaction variables
In addition to pressure, temperature and gross
composition of the reaction mixtures other influences which direct the course of reaction are
important. These include:
(a)
(b)
(c)
(d)

The major role of OH- as mineralizing 'catalyst'.

Structure directing effects of cations.
Use of organic bases.
Directing effects of anions other than OH-, and
role of added salts.
(e) History-dependent effects such as:
(i) the ripening period of the reaction mixture;
(ii) whether the mixture is stirred or not
during zeolite formation;
(iii) the physical and chemical nature of the
reactalTtS; and even
(iv) the order in which reactants are mixed.
Some comments on these variables follow.

Mineralizing role of OHThe OH- ion is a good complexing agent which

can, through this property, bring amphoteric
oxides and hydroxides into solution, but which

Zeolites and their synthesis: R. M. Barrer

Thirdly, if the concentration of OH- (as KOH)

was kept constant but the absolute a m o u n t of
KOH was increased by increasing the volume of
the KOH solution added, the yields of crystals
declined, as shown in Figure 2 s. The two solutions
were 1 M in KOH (yielding chabazite-type zeolite)
and 6 M in KOH, (yielding edingtonite type
zeolite). Thus the solution retains unreacted but
dissolved species in amounts increasing with the
volume of alkali hydroxide taken. The zeolites
thus show a solubility in their alkaline m o t h e r
liquor.

0
)n
c:
10

\D

I
1

I
I
I
~
3
5
M o l a r i t y of KOH solution

I
7

I
9

Figure 1 Effect of K O H s o l u t i o n c o n c e n t r a t i o n on t h e silica : a l u m i n a

ratio (n) of the crystallization p r o d u c t s s.

Although metastable phases often precede their

more stable successors, if the metastable phase is
isolated from its mother liquor it can remain
unchanged indefinitely thereafter. This is of major
significance in zeolite chemistry because it allows
one to manufacture such species as faujasite
(zeolites X and Y), metastable with respect to
zeolite Na-P (gis~ondine type). Likewise with
zeolite A which has not been found in Nature at
all.

14

1.0

&

bu
"5
~@0.6
q)
0.2

20

60

Fourthly, increased concentration of OH- can

accelerate crystal growth and shorten the induction
period before viable nuclei form. This is shown in
Figure 3 sl for the formation of mordenite from
amorphous aluminosilicate at 300C. The decreasing yield at pH 13.3 is due to progressive transformation of the mordenite initially formed into
the more stable product (under the experimental
conditions), analcime. This is an example of
Ostwald's law of successive transformations, in
which a metastable phase appears first and then
successively more stable phases replace it and
each other. The formation of the mordenite was
followed using sorption of nitrogen to measure
yields of crystals.

"~K-F

100
140
180
220
c m 3 o f KOH
Figure 2 E f f e c t of ratios of m e t a k a o l i n i t e : K O H s o l u t i o n o n t h e
v i e l d of crystallization p r o d u c t s , o, 1 M K O H ; zx, 6 M K O H s

does not yield such stable complexes that further

reaction involving them is prevented. Solution
permits ready mixing of the complexes formed,
examples of which include:
AI(OH)3 + OH- ~- AI(OH)4
A1203 + 3H20 + 2OH- ~ 2AI(OH)~
SiO2 + 2OH- ~ S i O ~ - + H20
3SiO 2 + 2OH- --- Si30 ~- + H20
ZnO+ OH- ~ ZnO(OH)Secondly, starting with silica-rich mixtures, the
greater the OH- concentration the more nearly the
ratio SiO2/A1203 approaches 249,50. This is shown in
Figure i so for some parent gels K20 , A1203,
nSiO 2 + excess KOH + aq. The final products were
primarily K-G (chabazite type) and K - F (edingtonite type). When SiO2/A1203 is two the A1 and Si
should alternate according to Lowenstein's AI-O-A1
avoidance rule. Thus by increasing OH- concentration the tendency to ordering of Si and A1 on
tetrahedral framework sites is also increased.

The decrease in nucleation time with rising pH

shown in Figure 3 can be attributed at least in
part to the m u c h greater concentrations of
reactants dissolved by the alkali. This helps germ
nuclei to grow more quickly from the more
numerous encounters between precursor species
in solution. The enhanced rate of growth after
nucleation might be explained in the same way:
the greater concentration of dissolved precursor

u0

E
20

pH 12.85
,~

eo

10-

f-

~ u ,~o o
~..... ~

pH 11.5

..-.-

?/-7\.,/

,-V/ /,,.
"\

-o
<

pH 12.5
~..x-

Ix

H13.3

//~

0
0

-.~

pill1

pHlO.2

-.~~-,"~n
16

24

Time ( h )

Figure 3 influence of pH on the crystallization rate of mordenite at

3 0 0 C f r o m a m o r p h o u s c o m p o u n d s~

ZEOLITE& 1981, Vol. 1, October 133

Zeolites and their synthesis: R. M. Barrer

Table5 Solubility of quartz (gdm -3) in NaOHandNa2CO 3
solutions s2
Temperature
(C)

Na~O (wt %)

300

1
5
15
1
5
15
1
5
15
1
5
15

350
400
450

Solubility in:
NeOH aq.

Na2CO 3 aq.

20
135
514
25
152
515
35
155
560
35
163
560

5
28
48
13
50
60
22
90
105
24
124
285

species allows faster transport to the surfaces of

growing crystals, a higher concentration at the
surface and faster surface reaction to extend the
crystal lattice. The striking way in which the
solubility of quartz increases with concentration of
NaOH or Na2CO 3 is illustrated in Table 5 s2. in
distilled water the solubility of quartz at 1 atm and
25C has been estimated to be s2a 6 ppm.
Finally, one notes the sigmoid form og the kinetics
curves of Figure 3, which are characteristic of
zeolitization kinetics in general and will be considered in more detail later.

Structure-directing role of cations

The cations in the reactant mixtures have been
found to determine or influence the kinds of

zeolite which form. Table 6 indicates those cation

environments which, in m y laboratory, have
tended to yield certain zeolites. Among other
factors such as total alkalinity, temperature and
overall composition one may make the following
observations.

(i) Sodic environments favour the formation of

sodalite and cancrinite hydrates, gismondine types
(Na-P), gmelinites, faujasites and zeolite A. Sometimes the combination of a small and a large cation
serves the same function as an ion of intermediate
size. Thus zeolite A was formed in the+presence of
(Li + + Cs + + TMA +) as well as with Na alone.
(ii) Mordenite formed in sodic, calcic and
strontium-containing environments; the analcime
topology was also obtained in a range of cationic
environments and so were edingtonite-type and
phillipsite-type zeolites.
(iii) Chabazite and zeolite L formed in potassic
media while Li-ABW and Li-H were favoured b y
lithic environments. Various other zeolites (types
related to thomsonite, epistilbite, heulandite,
ferrierite, yugawaralite and also Ba-J and Ba-K)
appeared in media containing alkaline earth metal
cations.
(iv) Some zeolites formed best in the presence of
two or more cations, examples being zeolite EAB
(TMA-E), offretite and mazzite (zeolite 2) all of
which were favoured by Na + NMe~ mixtures.

Table 6 Zeolite syntheses in relation to cation environments*

Zeolite

Cations in reaction mixture

Preferred cations

Gismondine types
Gmelinite types
Faujasite types
Zeolite A types
Zeolite (Na, NMe4)-V
Sodalite hydrates
Cancrinite hydrates
Zeolite EAB~ (TMA-E)
Mazzite type (zeolite 12)
Offretite types
Mordenites
Analcimes and isotypes

Na, (Na, NMe4) , (Na, Li), (Na, K), (Na, Ba), (Li, Cs, NMe 4)
Na, St, (Ca, NMe4), (Na, NMe 4)
Na, (Na, NMe4), (Na, Li), (Na, Ba)
Na, (Na, NMe4), (Na, K), (Na, Ba), (Na, Ba, NMe4), (Li, Cs, NMe 4)
Na, (Na, NMe 4)
Na, NM%H, NMe4, (Na, NMe4), (Na, K), (Na, LI), (Ca, NMe4), (Li, Cs, NMe 4)
Na, (Na, Li), (Na, NMe4), St, (Li, Cs, NMe 4)
(Na, NMe 4)
(Na, NMe 4)
(Na, K, NMe4) , (Na, Ba), (Na, Ba, NMe4), (Li, Cs, NMe 4)
Na, Ca, Sr
Na, K, Rb, Cs, TI, NH4, Ca, Sr, (Na, K), (Na, Rb), (Na, Cs), (Na, TI), (K, Rb),
(Rb, TI), (Li, Cs)
K, Rb, Cs, (K, Na), (Na, Li), (K, Li), (Li, Cs, NMe4), (Ba, Li), (Li, Cs)
K, Ba, Ca, NH4, NMeH3, NMe2H~, NM%H, NM%, (Na, K), (Na, NMe4),
(Ca, NMe4) , (Na, Ba)
K, St, (K, Na), (K, LI), (K, Ba), (K, Na, NMe 4)
(K, Na), K, Ba, (Ba, K), (Na, Ba)
Ca
Ca
Sr
Sr
Sr, (Ba, Li)
Ba
Ba, (Na, Ba), (K, Ba), (Li, Cs, NMe 4)
Ba
Li, (Li, K), (Li, Na), (Li, Cs, NMe 4)
Li
(Li, Cs, NMe 4)

Na
Na
Na
Na
Na
Na
Na
(Na, NMe 4)
(Na, NMe 4)
(Na, K, NMe 4)
Na, alkaline earth ions
Various

Edingtonite types
Phillipsite types
Chabazite types
Zeolites L
Thomsonite type
Epistilbite type
Heulandite type
Ferrierite type
Yugawaralite type
Zeolite Ba-J
Zeolite Z K - 5 t y p e s
Zeolite Ba-K
Zeolite Li-ABW
Zeolite Li-H
Zeotite ZSM-2 type

K, Rb, Cs, Ba
K and others
K
K, Ba
Ca
Ca
Sr
Sr
Sr, Ba
Ba
Ba
Ba
Li
Li

* The examples in this table are taken mainly from the series Hydrothermal Chemistry of Silicates, Parts 1 to 22, and on Chemistry
of Soil Minerals, Parts 1 to 14, published in the J. Chem. Soc. (London), from 1951 onwards. Results from some earlier papers
from the author's laboratory are also included.
Originally considered to be like erionites 35, but recently shown to have a novel structure 53.

134 Z E O L I T E S , 1981, Vol. 1, October

Zeolites and their synthesis: Ft. i14.Barrer

The results in Table 6 in no way exclude the possibility that a given zeolite topology may result from
still more varied cationic compositions, or by
different chemical pathways. The KFI (i.e. ZK-5)
framework provides an example of synthesis b y
varied pathways. It was first made in 194831 b y
recrystallizing analcime with excess BaC12 or
BaBr 2 plus a little water (Species P and Q). Later
it was made s4 from aluminosilicate gels with NaOH
+

aq. plus the organic base C%N~NC%]IOH-) 2

Still later it was made from aluminosilicate gels
with aqueous KOH + CsOH in particular proportions ss, and finally from NMe4-aluminosilicate
solutions with LiOH + CsOH s6.

Influence of salts in zeolite formation

Water is not the only guest species which can enter
zeolites during, and which assists, syntheses of such
open framework aluminosilicates. Inorganic salts
can appear encapsulated in certain natural minerals
(the sodalite-nosean group, cancrinites, scapolites
and afghanite and related minerals) as well as in
Species P and Q (KFI framework) and in K - F
(edingtonite type zeolite). The salts occupy some
or all of the same intracrystalline channels and
cavities as water molecules, and they can support
and stabilize these frameworks. In general the salt
molecules are difficult to remove, though this is
possible for such open structures as the KFI
framework of Species P.
The salts may cause formation of specific zeolites.
Thus, as already noted, excess BaC1z or BaBr 2
acting hydrothermally on analcime converted it to
Species P and Q, while excess KC1 and KBr converted analcime to salt-bearing forms of the edingtonite structure (Species N and O) sT. Also salts
determined which of the frameworks of sodalite or
cancrinite would form ss,59. Alumina and silica
were provided as metakaolinite, A120 3 2SiO z.
4 M NaOH aq. was normally used together with
salts in amounts which were systematically varied.
The reaction temperature was usually, b u t not
always, 80C. It was observed that:
(a) The yield could be improved by the presence

of salts. Thus in absence of salt the metakaolinite

(MTK) with 4 M NaOH gave 53% of the theoretical
yield of sodalite hydrate, while MTK with 4 M
NaOH and 0.5 M NaC104 gave a yield of 96%.
(b) Apart from increasing the yield, the X-ray
patterns of b o t h sodalite and cancrinite were often
sharpened when salts were included, suggesting
better crystallinity.
(c) The salt anions had, as noted above, a structuredirecting effect, in that at 80C certain salts caused
cancrinite and others caused sodalites to appear
(Table 7). At high temperatures, e.g. 300-450C,
and in the case of basic sodalite and cancrinite the
concentration of NaOH also had an influence:
200-300% excess NaOH yielded basic sodalite
(sodalite hydrate); above 300% excess NaOH basic
cancrinite (cancrinite hydrate) replaced the
sodalite 32.
(d) As Table 7 indicates, the thermal stability in
d.t.a, depended upon the kind of salt present, and
also upon the amount of the given salt included
within the framework. When all other variables
were kept constant (i.e. amount of MTK, concentration of NaOH, amount of water, temperature
and pressure) b u t only the salt concentr~rtions were
varied, continuous isotherms of salt uptake vs. concentration were obtained (Figure 4s8). As more
salt was taken up, zeolitic water and caustic soda
were pro~essively displaced. Each 14-hedral
sodalite cage is filled by 4 water, 2 caustic soda
or 1 salt molecule. Each cage is thus a four-fold
site for water, two-fold for NaOH, and a single
site for the salt. The salt isotherms arc of Type I
in Brunauer's classification, as Figure 4 indicates.
Based on detailed balancing ideal mixture isotherms for each species in the water, NaOH, salt
mixture could be derived, which with reasonable
assignments of adjustable parameters could reproduce the curves of Figure 4 reasonably well.

IA
20.01

F
if,,"

Table 7 Structure-directing effect of some salts, and thermal

stability of salt-filled sodalites and cancrinites s8
Stability in d.t.a.

Sodalites

Cancrinites

Stable above 850C

Na2SO 3 (Na2SO 4)

Na2SO4

Stable at ~ 850C

NaCl
NaBr, Nal

Na2SeO4

Lattice breakdown at -- 850C

NaOH
CH3COONa
Na2CO 3
NaHCO 3
Na2C204
Na2WO 4
Na3PO 4
NaCIO 4
NaCIO 3
Na2S

NaOH
Na2CrO 4
NaNO3
Na2MoO 4
Na2FeO 4
NaMnO 4
Na2VO 4
NaJeO 4
NaN 3

~1oo

i i t ~

. _ _ _ . _

0
0

Concentration of satt in synthesis solution (M)

Figure 4 Salt and water inclusion isotherms in sodalite. Synthesis
conditions: 80C, 4 M NaOH, crystalline kaolinite feedstock.
A, NaCIO4; B, NaCtO3; C, NaBr; D, NaCI; E, H20 (NaBr isotherm);
F, H20 (NaCI isotherm); G, H20 (NaCIO 3 isotherm); H, H20
(NaClO 4 isotherm) ss

ZEOLITE& 1981. Vol. 1. October 135

Zeolites and their synthesis: R. M. Barrer

Zeolite growth in presence of organic bases

Table 6 contains examples of zeolitization in

300

presence of organic bases. The use of such bases

was pioneered in 19 616 with the re sults summarized
below:
+

NH+
4
NH4-analcime
NH4-harmotome-type
NH4-mica
NM%H

N-harmotome-type
N-mica

NMeH3

NMe2H=

20~

N-harmotome-type N-harmotome-type
N-mica
N-mica

1/

N -T

+
NMe

-/1\

N-harmotome-type
N-sodalite
N-Q (zeolite A)
N-R (faujasite-type)
N-montmorillonite

The crystallization fields in the NMe4OH + aluminosilicate gel system is shown in Figure 5. The
symbol 'N' denotes 'containing alkylammonium
and/or ammonium ions', since under the synthesis
conditions alkylammonium ions may partially
hydrolyse. It was predicted, and found, that when
large ions such as l~Me 4 are incorporated the
zeolites produced are more silica-rich than usual,
because only a limited number of these ions could
be fitted into the pore space available in the
framework and therefore the anionic framework
charge would necessarily have to be low (more
Si, less M).
The use of organic bases for zeolite synthesis has
since been developed extensively, some results
being given in Table 8. The formation of silica-rich
zeolites culuminated in forms of ZSM-5 and
ZSM-11 which contain only traces of A1 (the
so-called silicalites 167 and 268). These limltin_g
compositions are porous crystalline silicas, like the
natural porous crystalline silica, melanophlogite 69,
which has the framework structure of clathrate
hydrates of Type 1. Their existence raises the
question whether other zeolite topologies can be
obtained as the M-free silica end-members. Acid

~-I0~
8
E

3od
N-V

0c

100

I
2

4
Mol ratio ( n )

Figure 5 Crystallization fields o f nitrogenous aluminosilicates

derived f r o m t e t r a m e t h y l a m m o n i u m aluminosilicate gels 6. N - A =
boehmite; N - T = sodalite type; N-P = harmotome type; N - Q =
zeolite A type; N - R = faujasite type; N - V = m o n t m o r i l l o n i t e type

extraction of framework A1 has proved possible

for siliceous zeolites such as mordenite, ferrierite
and clinoptilolite, b u t this necessarily leaves behind
frameworks which, although still crystalline to
X-rays, are nevertheless rich in defects.

Nature and pre-treatment of reactants

Striking changes can arise in the products of
crystallization according to the physical nature of
reactants of the same overall composition, and to
the prior history of the reactants. This behaviour
emphasises that the products are often determined
b y non-thermodynamic factors such as nucleation

Table 8 Some zeolite syntheses in presence o f organic bases

Cations

Zeolite type

Cations

T e t r a m e t h y l a m m o n i u rn + (TMA+) 61

Gismondine

Na, K + b a n z y l t r i m e t h y l a m m o n i u m +65
[40

Na + + T M A + ~s,38,6o,62,63

Sodalite
Gismondine
Sodalite
Cancrinite
Zeolite A (isotypes
( N - A , ~, Z K - 4 )
Faujasite

Ca(?+ + T M A + 64

Ba=+ + T M A + 34
K + + Na + + T M A + 35

Zeolite EAB
Mazzite (zeolite ~,)
Zeolite (Na, NMe4)-V
(isotypes N and Z - 2 1 )
Gismondine
Sodalite
Gmelinite
Erionite-type
Zeolite L
Erionite-type
Offretite
Chabazite

136 ZEOLITE& 1981, Vol. 1, October

Na+ + I

Zeolite type

)~1(

Na + + < ~ > ~ 1 (

Erionite
Losod

]40

Losod

Na + + n e o p e n t y l t r i m e t h y l a m m o n i u m + 4o Losod
+
6~
Na + + N ( ~ N C H 3
Levynite ( Z K - 2 0 )
+
+
Na + + C H 3 N ~ N C H 3 s4
Zeolite Z K - 5
Na + + t e t r a p r o p y l a m m o n i u m + 42
Na++ t e t r a e t h y l a m m o n i u m + 43
Na + + t e t r a b u t y l a m m o n i u m + 45
Na + + b e n z y l t r i p h e n y l a m m o n i u m + 4s
Na + + t e t r a b u t y l p h o s p h o n i u m + 4s
+
+
K+-~ C H 3 N ~ N C H a

Zeolite
Zeolite
Zeolite
Zeolite
Zeolite

ZSM-5
ZSM-8
ZSM-1 1
ZSM-1 1
ZSM-1 1

Zeolite Z S M - 1 0

Zeolites and their synthesis: R. M. Barrer

kinetics, governed by fluctuations which cause

various precursor species and germ nuclei to appear
and disappear. For example when the sources of
alumina and silica were respectively kaolinite
(oxide formula A1203.2SiO2.2H20) and metakaolinite (oxide formula A1203.2SiO2), with or
without added silica, and the mineralizing solutions
were aqueous Ba(OH)2 + LiOH the products at
80C wereT0:

From metakaolinite
(Li, Ba)-ABW, zeolite
(Ba, Li)-edingtonite
(Ba, Li)-edingtonite type
(Ba, Li)-G, L (like zeolite LTL)
(Ba, Li)-M (phillipsite type)
(Ba, Li)-N (unidentified)
From kaolinite
(Ba, Li)-Q (yugawaralite type)
(Ba, Li)-P* (non-zeolite, like cymrite)
(Ba, Li)-T (barium silicate hydrate)
The products from metakaolinite were thus
completely different from those obtained from
kaolinite.
When soluble silicates are a source of silica in
synthesis of faujasites (zeolites X and Y) it has
been found that reaction proceeds much more
easily when there are traces of A1 in the sodium
silicate 71,72. This strongly suggests aluminosilicate
precursor species in the silicate which in solution
assist nucleation of faujasite. Further evidence of
the existence of precursor species was obtained in
synthesis of analcimes from dilute solutions containing proportionately very little A1 as compared
with Si and NaOH 7a. The analcimes were much
richer in A1 than the parent solutions and the
composition of a given analcime did not alter with
time as crystallization proceeded up to complete
exhaustion of the A1. This was taken to indicate
that the crystals grew from solution only from
dissolved aluminosilicate species of fixed compositions which could vary only with the
NaOH : A1 : Si ratio in the initial solution.

Kinetics of crystal formation and growth

As shown in Figure 3 the total weight of crystals
produced plotted against time follows a sigmoid
curve. There is an induction time, a period of
accelerating deposition of crystalline material and
finally a period of decline in this deposition as one
or more of the essential nutrient reactants is used
up.
Nucleation
In the period before viable nuclei appear one may
consider that, by fluctuation, various aluminosilicate germ nuclei appear and disappear. Cations,
with or without their hydration shells, may
influence these processes (Table 6) by acting to
some degree as templates for forming germ nuclei.
This should be particularly apparent with the large
organic ions (Table 7). Also, some cations have a

structure-breaking effect on the H-bonding in

water and some a structure-forming role. Among
the latter are ions like NMe~. Eventually, after a
sufficient time has elapsed, one or more kinds of
germ nucleus may reach the critical size to become
viable and crystal growth begins. An example of
this is found in the low temperature 'ripening'
period often allowed in synthesis of faujasite
zeolites X or Y where the low temperature favours
a good concentration of the germ nuclei needed
for the ultimate crystallization as faujasite. By
subsequently raising the temperature some of the
germ nuclei develop into viable nuclei and crystallization proceeds.
The reason why germ nuclei must reach a critical
size before becoming viable for crystal growth can
be considered in general terms as follows. In a
liquid phase there must be an interfacial free
energy, Agl, between the nucleus and the
surrounding medium. This is a positive term, which
thus tends to render the germ nucleus unstable.
However, in absence of Ag1 there would only be a
negative free energy of formation Agi for a
potentially viable germ-nucleus, composed o f j
structural units. The term Ag1 will be proportional
to the area of interface between the germ nucleus
and liquid and so to j2/3 while Agi will be proportional to - j . Thus the nett free energy of
formation is:
Ag 2 = Aj 2/3 _ Bj
where A and B are coefficients. Whether Ag2 is
positive or negative then depends on the values of
Aj 2/a and Bj. Initially, f o r j small, Ag 2 is thought
to be positive (Aj 2/3 > Bj) and such germ nuclei
produced by fluctuations are not stable (Ag 2
positive) and tend to disappear. However, such
fluctuations may eventually also give a proportion
of germ nuclei with larger j. If some of these reach
the size where:

dj

- O, i.e. where: j = \~-~]

then any further addition of structural units will

result in decreasing Ag2. There is thus eventually a
current of germ nuclei through the critical size so
that they are now viable nuclei on which crystal
growth takes place. This situation is represented
formally in Figure 6 in which Ag2 is plotted against
j. Once the m a x i m u m in Ag 2 is reached the germ
nucleus has become viable in that further growth is
accompanied by a free energy decrease.

Post-nucleation stage
The rate of deposition of crystalline material on
the surface of growing crystals of zeolites A and X
has been measured by observing the dimensions of
the largest crystals at various times after the start
of heating the reactant gels 74. The linear crystal
growth rate can be determined as 0.5 Al/At where
Al is the increase in crystal dimension in time At.
Figure 7 shows that this growth rate is independent
of time over a considerable period, i.e. crystalline

ZEOLITES, 1981, VoL 1, October 137

Zeolites and their synthesis: R. M. Barfer

surface, for which E would correspond approximately with that for the viscosity of solution, i.e.
be - 16-17 kJ mo1-1. Accordingly it seems likely
that crystal growth is controlled by a chemical step
in which aluminosilicate units add to the growing
surfaces by condensation polymerization involving
elimination of water between appropriate pairs of
terminal OH groups. This mechanism requires a fit
between the terminal - O H groups of the surface
and those of the unit which is being added to the
surface.
Ag 2 0

The following procedure was used to reproduce the

experimental sigmoid curve of amount of N a - X
formed as a function of time 74. From the final
yield of crystals a histogram of size distribution
was prepared from a sample of 300 crystals. If
ni is the number of crystals in the i TM mode then
the fraction o~i = ni/N where N is the total number
of crystals. ~[he linear growth of the largest crystals
is shown in curve 1 of Figure 8. The linear rate of
growth remained constant for ~ 115 h and thereafter decayed asymptotically to zero. It was
assumed that prior to the decay period, crystals of
all sizes grew at the same linear rate, and that in
the decay period, crystals of all sizes still grew at
the same, though declining, linear rates. Thus the
time of nucleation, or the time at which crystals
of any given size range in the final product begin to
grow, can be determined. This in turn allows one
to find the nucleation kinetics (curve 2 in Figure 8).
Finally, the ratio Zt/Zf can be found, where Z t
is the mass of crystals at time t and Zf the mass in
the final product:

Figure6 Formal representation of the shape of the curve of Ag~

against the number, j, of structural units in a germ nucleus

3O

Zt

v.r

E is?
i

10

70

6
8
t (days)

10

where di is the mean diameter of crystals in the i th

12

14

Figure 7 Rates of growth at a series of temperatures in C of the

largest crystals of zeolite Na-X from aluminosilicate gels 74

40

,100
-

90
80
7O

material is laid down at a constant rate. Starting

with a reaction mixture of oxide composition 4.12
Na20, A1203, 3.5 SiO2, 593 HzO the linear rates
were for X:
70C
80C
90C
100C

0.0175 pm/h
0.0375 #m/h
0.0625 #m/h
0.1071 #m/h

6o
20

~o

40 0o

30
10
2O
10
O

These values give an Arrhenius activation energy,

E, of 62.5 kJ mo1-1. For zeolite A this energy was
43.7 kJ mol-L Both values are t o o high for control
b y diffusion of chemical nutrient to the crystal

138

ZEOLITES, 1981, Vol. 1, October

20 40

60 80 100 120 140 160 180 200 220 240

t(h)
Figure 8 Nucleation kinetics (curve 2) (ordinate = (As/At) X 102};
rate of growth of the largest crystals (curve 1, of Figure 7); and
total amount of crystals formed (curve 3) as a function of time TM.

Zeolites and their synthesis: R. M. Barter

4
5

30

25

7
8
9

"20
1.5

10
,,,,I

i
10-3

i , i,Jl
10 -2

l l l l I

it

10 -I

k (Si02)

Figure 9 Dependence of rate constants k' = k/[SiO2]soln on Si/AI

ratios of faujasites at 88 C 7s, k denotes the linear growth rate.

mode and di (t) is the mean diameter these crystals

would have had at time t. Vt and V/are volumes of
crystals at time t and finally, respectively. This is
curve 3 of Figure 8, which agrees in form with
the experimental curve..The above treatment does
n o t give information of events at the molecular
level. With reasonable physical assumptions it
shows that fresh nucleation occurs over the whole
period of crystallization, with a strong maximum
at an early time (~ 40 h) before any appreciable
mass of crystals has appeared.

Deposition on seed crystals

Seed crystals of a given zeolite, if introduced under
conditions appropriate for forming that zeolite,
increase in size as crystalline material is deposited
on them. This aspect has been examined for
faujasites in considerable detail 7s. In the range
of concentrations studied the linear crystallization
rate was proportional to the concentration of
silicate in the solution for final products of given
Si:A1 ratio. The rate constants for growth divided
b y the concentration of silicate were strongly
dependent on the Si : A1 ratios of the deposited
faujasite (Figure 9). The more siliceous the zeolite
the less rapid the deposition on the seed crystals
of zeolite X, b y several orders of magnitude in the
range 1.4 ~< Si/AI ~< 3.4.
CONCLUSION
This introduction illustrates a number of aspects of
zeolite synthesis, based partly on the author's
experience. Synthesis is an area of inorganic and
physical chemistry which has both academic
interest and industrial significance. The variety of
the aluminosilicate mixtures from which zeolite
crystals can develop and the difficulty of establishing the nature and structure of precursor species in
solution make it hard to understand events at the
molecular level. Nevertheless I hope that zeolite
synthesis will in the future be studied in increasing
depth.

11
12
13
14
15
16
17
18
19
20
21
22

23
24
25
26
27
28
29
30
31

32
33
34
35
36
37
38
39

40
41
42
43
44
45
46
47
48

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