PRODUCTION OF PURIFIED TEREPHTHALIC ACID (PTA)

SESSION:
2K20-2K24

PROJECT MEMBERS:

MALIK MUHAMMAD FIAZ 2K20-Ch.E-134

MUHAMMAD MUZAMMIL 2K20-Ch.E-139
GHAZAL FATIMA 2K20-Ch.E-209
MUHAMMAD ABUBAKAR 2K20-Ch.E-137

DEPARTMENT OF CHEMICAL ENGINEERING

NFC INSTITUTE OF ENGINEERING AND TECHOLOGY, MULTAN

1
 To express our thanks to all those who contributed in our ways to the success of this
study and made it an unforgettable experience for us.

To our ALLAH Almighty who is always there for us. Thank you for guiding us and
giving us strength in our daily life. Thank you for always looking for us and being there
for us. Thank you for making all of these happened and ended it with a good outcome.

DEDICATED to our beloved parents, who have been our source of inspiration and gave
us strength when thought of giving up, who continually provide their mortal, spiritual,
emotional, and financial support.

To our teachers who never failed to teach and guide us.

To our friends, brothers, and classmates who shares their words of advice and
encouragement to finish this study.

And lastly to my group mates. Thank you for guidance, strength, and team work.

DEDICATION
 CERTIFICATION OF APPROVAL

This is to certify that the research work presented in this thesis entitled “Production Of
Purified Terephthalic Acid” was conduct by Mr. Malik Muhammad Fiaz, Mr. Muhammad
Muzammil, Ms. Ghazal Fatima, and Mr. Muhammad Abubakar under the supervision of
Engr. Muzaffar Riaz, and approved by all the members of thesis committee.
No part of this thesis has been submitted anywhere else for other degree. This thesis is
submitted to Chemical Department, NFC Institute Of Engineering And Technology in partial
fulfillment of the requirements for the degree of bachelor of engineering in the field of
Chemical Engineering, and accepted by the Head of the Department Dr. Sadiq Hussain of
NFC Institute Of Engineering & Technology.
Student Name: Malik Muhammad Fiaz Signature: ___________________
Student Name: Muhammad Muzammil Signature: ___________________
Student Name: Ghazal Fatima Signature: ___________________
Student Name: Muhammad Abubakar Signature: ___________________

1) External Examiner: _______________________ Signature: ___________________

(Designation and office address)
_______________________________________

2) Internal Examiner: _______________________ Signature: ___________________

(Designation and office address)
_______________________________________

3) Supervisor: _____________________________ Signature: ___________________

(Designation and office address)
_______________________________________

4) Co-Supervisor: __________________________ Signature: ___________________

(Designation and office address)
_______________________________________

5) Coordinator: ____________________________ Signature: ___________________

(Designation and office address)
_______________________________________

6) HOD: __________________________________ Signature: ___________________

(Designation and office address)
_______________________________________

Date: ___________________________

3
 AUTHOR’S DECLARATION

I Malik Muhammad Fiaz, Muhammad Muzammil, Ghazal Fatima, Muhammad Abubakar

hereby states that my thesis titles Production Of Soda Ash is my own work and has not been
submitted previously by me for taking any degree from NFC Institute of Engineering &
Technology or any other degree awarding institute and to the best of my knowledge has not
been submitted by any other scholar for the same purpose anywhere else in the
country/world.
At any time if my statement is found to be incorrect even after my graduation, NFC Institute
of Engineering & Technology has the right to withdraw my BSc. Degree.

Name of Student: Malik Muhammad Fiaz

Name of Student: Muhammad Muzammil
Name of Student: Ghazal Fatima
Name of Student: Muhammad Abubakar

Date: ___________________________

4
 PLAGIARISM UNDERTAKING BY THE SCHOLAR

I solemnly declare that research work presented in the thesis titled “Production Of Purified
Terephthalic Acid” is my research work with no significant contributions from any other
person. Small contribution/help whenever taken has been duly acknowledged.
I understand the zero tolerance policy of the Higher Education Commission and NFC
Institute of Engineering & Technology towards plagiarism. Therefore as an author of the
above titled thesis declare that no portion of my thesis has been plagiarized and any material
used as reference is properly referred/cited.
I undertake that if I am found guilty of any formal plagiarism in the above titled thesis even
after award of Bachelor degree, the university reserves the rights to withdraw/revoke my
Bachelor degree and that HEC and NFCIET has the right to publish my name on the
HEC/NFCIET website on which name of students are placed who submitted plagiarized
thesis.

Student Name: Malik Muhammad Fiaz Signature: ___________________________

Student Name: Muhammad Muzammil Signature: ___________________________

Student Name: Ghazal Fatima Signature: ___________________________

Student Name: Muhammad Abubakar Signature: ___________________________

5
 ACKNOWLEDGMENT

We express humble gratitude and praise the one and only Almighty ALLAH, the creator of
universe, who is beneficent and most merciful, guided us in difficult circumstances, who
endowed us with the will to undertake this design project, and bestowed upon us the wisdom
and means to complete it.

Great respect to our Holy Prophet Hazrat Muhammad (S.A.W.S) who taught and inspired us
to learn from our Mother’s lap till the darkest halls of our grave.

We are highly thankful to our honorable project supervisor Engr. Laraib Abid, who provided
us with his guidance and a chance to work on such an interesting topic. Her constructive
suggestions, constant guidance and friendly attitude encouraged us to work in a better
manner.

Furthermore, we are very thankful to our parents, teachers, and friends, whose special
attention in their prayers helped us achieve success throughout our lives.

Finally, our library deserves a special mention whose wealth of book and journals on
Chemical Engineering made our task easier.

6
Table of Contents
1| Introduction 1
1.1.| Historical Background 2

7
8
 CHAPTER NO.1 INTRODUCTION

In 1846, French chemist Amedee Cailliot manufactured Terephthalic Acid (from Turpentine).

After World War II, importance of terephthalic acid was rapidly increased in industrial level.
The oxidation reaction between p-xylene with dilute nitric acid produced terephthalic acid.
Resistance of air oxidation occurs, by air oxidation reaction between p- xylene which further
gives p-toluic acid. The conversion of toluic acid to methyl p-toluate [(C6H4) (CO2H)2] and
further oxidation then converted to monomethyl terephthalate, and further esterified
converted to dimethyl terephthalate. The bromide -promoted oxidation of p-toluic acid to
terephthalic acid was announced by Mid-Century Corporation and ICI In 1955. This
innovation allows the conversion of p-xylene without the need to isolate intermediates to
terephthalic.

Commercially production of terephthalic acid occurs, by oxidizing para-xylene with

oxygen which consists of acetic acid and dissolved catalyst in a liquid phase. The water
and acetic acid drawn from the reaction as a vapor stream causes the control lance of the
temperature and concentration of water produced as a byproduct in liquid phase. The
returning of reaction take place by removing of water enriched in acetic acid from at least
part of stream. The product of terephthalic acid which gives the crystals slurry in term of
liquid phase consists of acetic acid and impurities. In terms of centrifugation or filtration
process, TPA may distilled in liquid phase. At higher temperature acetic acid dissolved in
water and removed from liquid stream. Organic impurities removed from water in the
presence of hydrogen which gives the pure product. The production of terephthalic acid in
reaction medium containing oxidizing para-xylene with acetic acid which gives slurry on a
moveable band of filter material. In first zone, wet deposit produced from reaction medium
of slurry. The product of first wet deposit zone send to the second wet deposit, the removal
of second deposit send to third zone, in terms of second zone removal of aqueous medium
and slurry of TPA. Further purification of TPA preferred in purification plant.

In the reaction control temperature and water content for the removal of acetic acid in
reaction medium by step evaporation. At last part of distillation water will be removed
from the mixture and acetic acid leaving with lower water content. The acetic acid
recovered from water by oxidation step.

9
Historical Background:

The resin saponified by the potassium carbonate was precipitated by means of a warm
solution of ammonia; Cailliot named it abietic acid. This acid resin was slightly bitter; it
reddened litmus, was soluble in all proportions in alcohol, ether, and petroleum ether, and
neutralized by alkalis. Heated to 55
gujijokiagglomerated into transparent globules,
every similar to rosin. It combined with bases
losing about 5% of its weight as water. Cailliot
reported the preparation and properties of a series
of abietates (potassium, sodium, ammonium,
barium, strontium, calcium, magnesium, quinine,
and morphine). The abietates of sodium,
potassium, and ammonia, were non-
crystallizable; the latter was easily decomposed
Figure 1 Louis Armand Victor Amedee Cailliot
by heat. Quinine abietate was prepared by adding (1805-188840)

a neutral solution of ammonium abietate to another of neutral quinine sulfate. This salt was
white, flocculent, insoluble in water, very fusible, easily soluble in alcohol and ether but
not crystallizable from their solutions. Morphine abietate was prepared in the same
manner; it was a white flocculent solid, soluble in alcohol and ether; these solutions were
very bitter and non crystallizable (Cailliot, 1830).

According to Cailliot the essence of the turpentines of Abies pectinata and Abies excelsa
had an agreeable aromatic odor and hot taste; they were non-crystallizable, even at -20 oC,
and did not combine with alkalis. The neutral insoluble resins were little different one from
another; they were white, pulverulent, without a distinct crystalline form, dry to the touch,
tasteless and not acting upon litmus. They were insoluble in cold alcohol of 40o , in
petroleum ether, and in alkaline solutions. The neutral soluble resin (abietin) crystallized as
needles having a rectangular base; the faces were inclined along the axis, forming more or
less an elongated pyramid. Abietin was odorless almost insipid, insoluble in water and very
soluble in ether, naphtha, and acetic acid; it was very soluble in alcohol of 34o ; its
alcoholic solution has a slight bitter taste and did not act upon litmus and the violet syrup.
Upon melted it produced a white transparent liquid, which on cooling became white,

10
opaque and crystalline solid (Cailliot, 1830)

The volatile oils (essence) of Abies pectinata (Strasbourg) and Abies excelsa had the
following composition by weight percent in following table:

Table 1: Composition of the essences of Abies pectinata and excelsa

Turpentine from Abies Turpentine from Abies

pectinata excelsa

Volatile oil 33.50% 32.00%

Acid resin 46.3g 45.37

Abietin 10.85 11.47

Sub-resin (insoluble in 6.20 7.42

alcohol)

Extractive matter and 0.85 1.22

succinic acid

Loss attributed mainly 2.21 2.52

to the volatile oil

Figure 2 Turpentine Oil

Cailliot wrote that the sample of the turpentine of Abies excelsa that he had examined was

11
shady, slightly colored, had a bitter taste, and was less fluid than the one from Strasbourg.
It was very probably mixed with Abies pectinata. He also gave a detailed description of the
turpentine of Abies pectinata, Abies excelsa, Abies balsamea, Larix europea, and Pinus
maritima and sylvestris. According to Cailliot, scientists were undecided regarding the
question if vegetable resins were formed as such in vegetables or were the result of an
oxidation process of the essential oils. If this was so, could it possible to reproduce it in the
laboratory (Cailliot, 1846a, 1847)? In order to answer this question Cailliot subjected the
essence of turpentine to three different oxidation processes: (1) the slow action of air, (2)
the action of air under the influence of bases, and (3) the more rapid action of nitric acid
(Cailliot, 1846a, 1847). According to Cailliot, the reaction of nitric acid with the essence of
turpentine was vigorous and followed a complex route, but treating a small amount of
turpentine with a layer excess of acid diluted in water resulted in a calm reaction, easy to
follow in a distillation apparatus. The products of the reaction were numerous; abundant
sparkling nitrous vapors, together with CO2 , a substantial quantity of HCN, and a certain
amount of almost unaltered oil of turpentine. The latter had not changed its properties,
particularly its rotation power. Conrad Bromeis (1820-1862) and S. M. Rabourdin had
examined the mother liquor remaining in the distillation retort (Berzelius, 1843;
Rabourdin, 1844); Bromeis found it contained a new acid, which he named turpentinic
acid, and Rabourdin, oxalic acid and in several cases quadroxalate of ammonia (Cailliot,
1846, 1847). Cailliot stopped the controlled reaction after no more nitrous vapors were
formed and found that the residue contained two products, a mother liquor and a resinous
substance. The mother liquor was found to contain oxalic acid, HCN, which under the
operating conditions seemed to occupy the place of ammonium oxalate, and three new
acids. One of these acids had the formula C16H6 O8 = C16H4 O8 + 2HO, that is, it was an
isomer of the phthalic acid discovered by Auguste Laurent (1807-1853) (Laurent, 1836) in
the reaction between naphthalene and nitric acid. For this reason Cailliot suggested naming
it terephthalic acid (Je proposerai de le nommer acide téréphtalique).

Terephthalic acid was sufficiently distinct from phthalic acid, it was white, tasteless, and
insoluble in water, alcohol and ether; when heated a portion sublimed without losing its
hydrate water, while another portion decomposed into CO2 and benzene, C12H6 . The
acid was entirely converted into benzene and CO2 when heated with calcium hydroxide.
Nearly all the salts of terephthalic acid crystallized and burned readily, diffusing the odor
of benzene (Cailliot, 1846a, 1847).

12
The largest source of purified terephthalic acid is provided by the company name, “Lotte
Chemical Plant Ltd.” Terephthalic is used as a raw material in polyester industry. In
September 2009, Lotte “South Korea Conglomerate” attained the major shareholdings
in Pakistan PTA limited (PPTA). Eventually, the company name switch to “lotte chemical
plant LTD. In Pakistan petrochemical industry, Lotte chemical plant is the biggest source
of investment of about US $490 million. In Karachi, the plant at port Qasim was built
using ICI’ S state art of technology licensed in 1998. It provides the purified teraphthalic
acid (PTA) as a raw material to many industries i.e., textile and pet panicking industries.
The company has also created a large network at Qasim port vicinity. It includes the
chemical jetty, raw water pipeline and manufacturing of industrial glasses purified
terephthalic acid (PTA) is a key raw material in the production of polyester, particularly in
the manufacturing of polyethylene terephthalate (PET) resin for bottles, fibers, and other
applications. The production of PTA involves several historical and technological
developments.

Terephthalic acid itself is a white crystalline solid that was first synthesized in the 19th
century. The industrial production of PTA, however, gained prominence in the mid-20th
century as the demand for polyester products increased. The traditional method for
producing PTA involves the oxidation of p-xylene, a derivative of crude oil. This process
typically involves several steps, including catalytic oxidation, crystallization, and
purification. The development of more efficient catalysts and process optimization has
played a significant role in improving the overall yield and reducing the environmental
impact of PTA production. Over the years, researchers and engineers have focused on
refining the production processes to enhance efficiency, reduce energy consumption, and
minimize environmental impact. Advances in catalyst technology, reactor design, and
process integration have contributed to the evolution of PTA production. As global
demand for polyester continues to grow, the production of PTA remains a critical aspect of
the textile and packaging industries.

13
Ongoing research and innovation in sustainable practices are also shaping the future of
PTA production, with an emphasis on eco-friendly processes and raw materials. Purified
terephthalic acid (PTA) is a key raw material in the production of polyester, particularly in
the manufacturing of polyethylene terephthalate (PET) resin for bottles, fibers, and other
applications. The production of PTA involves several historical and technological
developments. Terephthalic acid itself is a white crystalline solid that was first synthesized
in the 19th century. The industrial production of PTA, however, gained prominence in the
mid-20th century as the demand for polyester products increased.

The traditional method for producing PTA involves the oxidation of p-xylene, a derivative
of crude oil. This process typically involves several steps, including catalytic oxidation,
crystallization, and purification. The development of more efficient catalysts and process
optimization has played a significant role in improving the overall yield and reducing the
environmental impact of PTA production.

Over the years, researchers and engineers have focused on refining the production
processes to enhance efficiency, reduce energy consumption, and minimize environmental
impact. Advances in catalyst technology, reactor design, and process integration have
contributed to the evolution of PTA production.

As global demand for polyester continues to grow, the production of PTA remains a

14
critical aspect of the textile and packaging industries. Ongoing research and innovation in
sustainable practices are also shaping the future of PTA production, with an emphasis on
ecofriendly processes and raw materials.

The plant for the production of terephthalic acid was Established in 2000, is a mutual
venture between Society general and the Spanish oil company, CEPSA. Located in the
soul of the industrial zone in east-end Montreal, the plant has been working since
September 2003.

The first plant of its kind in Canada, had to find itself fast in North America. Its
gathering exports to the United States also put it daily ground with other major producers
in the industry. In enormous part, the company’s quick, efficient growth was made feasible
through strategic management, which allowed it to meet the rising market.

The intention of the city’s east end as the location for CEPSA was a strategic one. Being in
close proximity to other petrochemical facilities helped build synergy and allow for
practical partnerships between the various plants that make up the polyester production
line. The chain of production rests on the dynamic, creative links developed by the group
of petrochemical and chemical plants founded in eastern Montreal to promote local
manufacturing using raw materials available in Quebec.

15
The production line consists of the following components:

Petroleum – Xylene – Para-Xylène – PTA – PET.

It is an industry in which it is the prevailing player and one where the need from industrial
consumers nowadays over extends household production ability. Yet Lotte Chemical
Pakistan wants to stay for the purified terephthalic acid (PTA) industry to develop before it
invests in capability growth, according to its management.

During an analyst briefing declaring openly the details of the company’s economic results
for the third quarter of calendar year 2019, Lotte Pakistan’s management said that they
could only illustrate investments in capacity growth if they could expand capacity to
800,000 tons, up from the existing 500,000 tons that their factory established in Port Qasim
can produce.

Purified terephthalic acid (PTA) is an important raw material utilized in the production of
polyester fiber and polyethylene terephthalate (PET) plastic bottles. Lotte Chemical
Pakistan Ltd considers itself a world-class supplier of PTA. A trendsetter in industrial
acquisition in Pakistan, Lotte’s PTA plant was constructed in 1996 to 19997 and started
production in June 1998.

The company began its presence as an assistant of ICI Pakistan in 1995, before being spun
off as a self-reliant entity in 2000 named Pakistan PTA. In 2008, Akzo Nobel, the Dutch
chemical giant purchased ICI worldwide and briefly evolved the parent company of
Pakistan PTA. In September 2009, the company was paid for by the South Korean
conglomerate Lotte, and obeying the name of the company was transformed to its current
name.

Last year in 2018, the company managed to create at more than 100% of capacity, turning
out 516,000 tons of PTA, despite their declared ultimate capability of 506,000 tons. One
would assume after smashing this mark, the company would yearn to go ahead, and in fact,
evaluate expanding its capability and taking over some of the percentage that imports hold
on the PTA market.

Pakistan’s existing PTA market share is around 800,000 metric tons whereas Lotte
Chemical’s has a capacity of 500,000 tons and the remainder of the market is existing met
by imports composed research analysts at BIPL Securities, a securities brokerage firm, in
an analysis letter published to clients on November 22.

16
As per the administration, future PTA growth relies mostly on market growth and
development of polyester staple fiber (PSF) and filament yarn market that are nowadays
operating at 79% utilization level, wrote the BIPL analysts. Presently, the company does
not have any agendas for growth, however, should the necessity for PTA crosses 1 million
tons, Lotte would expand by 800,000 (at an estimated cost of $400 million) which would
carry the in rated ability to 1.3 million tons per annum.

However, while the company is not yet ready to leap into an expansion, there does appear
to be room for optimism for the PTA industry, which has seen demand increase over the
past three years, particularly from textile manufacturers.

Demand for PTA increased notably during 2015-2018 owing to improved power supply to
textile customers of Lotte (75% of the total customer base). This was also reflected through
improved an polymer operating rate (capacity utilization of textile customers) from 69% in
2015 to 89% in 2018. However, the operating rate is expected to reduce to 79% during the
current year.

The reason Lotte is referring to the deceleration in need in 2019 is the enactment of the
new computerized nationwide identity card (CNIC) condition for purchasing products
above the marketing value of 50,000, which has impeded the capacity of casual dealers and
unregistered manufacturers to purchase their product.

According to Lotte, the justification they will be shutting down the year at under 500,000
tons of production in 2019 is that the new CNIC necessity has implied a decline in the
market of PTA, especially in Punjab, which was easily their biggest demand.

Nonetheless, the company management of Lotte Pakistan is confident that the company

17
would regain 100% capacity come next year in 2020. However, this is still not indicative
of the expansion that the government would like to reduce the imports that are making up
for the remaining demand at the moment.

But with the CNIC regulations set a take full effect in February 2020, along with the
company setting aside Rs5.0 billion for GIDC provisioning, and the company’s Port Qasim
plant set to be closed for maintenance for 15-20 days in March 2020, the road ahead maybe
not necessarily bumpy but is also not facilitative to the expansion that the government
would desperately love to spruce up their number

Meanwhile, the company does predict margins to enhance relatively over the attaining
calendar year. “The management expects PTA margins to enhance from existing $90 per
ton to $110-140 per ton during 2020”.

Physical And Chemical Properties Of Raw Materials:

 Paraxylene
 Acetic Acid
Paraxylene:
Basically, purified Terephthalic acid is formed by a reaction between paraxylene (PX) and
acetic acid. Polymerization process is used to create PET (polyethylene terephthalate) by
utilizing PTA p-xylene (para xylene) is an aromatic hydrocarbon. It is one of the isomers of
dimethylbenzene called as xylenes. The p- used for (para) demonstrate that two methyl
groups in p-xylene occupy the diametrically opposite substituent positions 1 and 4. It is in
the position of the two methyl groups, o-xylene and m-xylene. All have the same chemical
formula. C6H4(CH3)2. Their isomers are colorless and highly flammable. Polyethylene
terephthalate also combine with other chemicals to form polyester.

Paraxylene, often abbreviated as PX, is an aromatic hydrocarbon compound. It's one of the
three isomers of xylene, the other two being ortho-xylene and meta-xylene. These isomers
differ in the arrangement of carbon atoms around the benzene ring.

Paraxylene is primarily used in the production of purified terephthalic acid (PTA) and
dimethyl terephthalate (DMT), both of which are key intermediates in the manufacturing of
polyester. Polyester is widely used in the production of fibers, films, and resins for various
applications, including clothing, packaging, and bottles.

18
 Table 1.1. Chemical And Physical Properties Of Paraxylene

Parameters Results

Chemical Formula C8H10

Appearance Colorless Liquid

Odor Aromatic

Density 0.866 g/mL

Melting Point 13.2 C (55.8 F; 286.3 K)

Boiling Point 138.35 C (281.03 F; 411.50 K)

Solubility In Water Insoluble

Solubility In Ethanol Very Soluble

Solubility In Diethyl Ether Very Soluble

Vapor Pressure 9 mmHg (20 C)

Magnetic Susceptibility -78.76 × 10-6 cm3/mol

Refractive Index 1.49582

0.73885 cP at 0 C
Viscosity
0.6475 cP at 20 C

Dipole Moment 0.00 D

Acetic Acid:
Acetic acid (CH3COOH) is a corrosive organic acid having a sharp odor, burning taste, and
pernicious blistering properties. It is found in ocean water, oilfield brines, rain, and at trace
concentrations in many plant and animal liquids. It is central to all biological energy
pathways. Fermentation of fruit and vegetable juices yields 2-12% acetic acid solutions,
usually called vinegar (qv). Any sugar-containing sap or juice can be transformed by
bacterial or fungal processes to dilute acetic acid.

Theophrastus (272-287 BC) studied the utilization of acetic acid to make white lead and
verdigris. Acetic acid was also well-known to alchemists of the renaissance. Andreas libavius
(AD 1540-1600) distinguished the properties of vinegar from those of icelike (glacial) acetic
acid obtained by dry distillation of copper acetate or similar heavy metal acetates. Numerous

19
attempts to prepare glacial acetic acid by distillation of vinegar proved to be in vain.

Lavoisier believed he could distinguish acetic acid from acetous acid, the hypothetical acid
of vinegar, which he thought was converted into acetic acid by oxidation. Following
Lavoisier’s demise, adept proved the essential identity of acetic acid and acetous acid, the
latter being the monohydrate, and in 1847, Kolbe finally prepared acetic acid from the
elements.

Most of the acetic acid is produced in the United States Germany, Great Britain, Japan,
France, Canada, and Mexico. Total annual production in these countries is close to four
million tons. Uses include the manufacture of vinyl acetate and acetic anhydride. Vinyl
acetate is used to make latex emulsion resins for paints, adhesives, paper coatings, and textile
finishing agents. Acetic anhydride is used in making cellulose acetate fibers, cigarette filter
tow, and cellulosic plastics

PHYSICAL PROPERTIES: Acetic acid, fp 16.635 C , bp 117.87 C at 101.3 kPa, is a

clear, colorless liquid. Water is the chief impurity in acetic acid although other materials
such as acetaldehyde, acetic anhydride, formic acid, biacetyl, methyl acetate, ethyl
acetoacetate, iron, and mercury are also sometimes found. Water significantly lowers the
freezing point of glacial acetic acid as do acetic anhydride and methyl acetate. The
presence of acetaldehyde or formic acid is commonly revealed by permanganate tests;
biacetyl and iron are indicated by color. Ethyl acetoacetate may cause slight color in
acetic acid and is often mistaken for formic acid because it reduces mercuric chloride to
calomel. Traces of mercury provoke catastrophic corrosion of aluminum metal, often
employed in shipping the acid.

The vapor density of acetic acid suggests a molecular weight much higher than the formula
weight, 60.06. Indeed, the acid normally exists as a dimer, both in the vapor phase and in
solution. This vapor density anomaly has important consequences in engineering
computations, particularly in distillations.

Acetic acid containing less than 1% water is called glacial. It is hygroscopic and freezing
point is a convenient way to determine purity. Water is nearly always present in far
greater quantities than any other impurity. Table 1.2 shows the freezing points for acetic
acid - water mixtures.

20
 Table 1.2. Acetic Acid – Water Freezing Points

Acid Acid, wt% Freezing Point, C

100 16.635

99.95 16.50

99.70 16.06

99.60 15.84

99.2 15.12

98.8 14.49

98.4 13.86

98.0 13.25

97.6 12.66

97.2 12.09

96.8 11.48

96.4 10.83

96.0 10.17

The Antoine equation for acetic acid has recently been revised.

ln(P) = 15.19234 + (-3654.622)/T + (-45.392)

The pressure P is measured in kPa and the temperature T in K. The vapor pressure of pure
acetic acid is tabulated in Table 1.3.

Table 1.3. Acetic Acid Vapor Pressure

Temperature, C Pressure, kPa

0 4.7

10 8.5

20 15.7

30 26.5

21
 40 45.3

50 74.9

60 117.7

70 182.8

80 269.4

110 776.7

118.2 1013

130 1386.5

140 1841.1

150 2461.1

160 3160

170 4041

180 5091

190 6333

Table 1.4. Density Of Acetic Acid

Temperature Density

20 1049.55

25 1043.92

30 1038.25

47 1019.19

67 996.46

87 973.42

107 949.90

127 925.60

147 900.27

22
 167 873.56

187 845.40

197 829.88

207 817.07

217 797.44

Acetic acid forms a monohydrate containing about 23% water, thus the density of acetic acid-
water mixture goes through a maximum between 77-88 wt % acid at 15%C. When the
water is mixed with acetic acid at 15-18, Heat is given off. At greater acetic acid
concentrations, heat is taken up. The measured heat of mixing is consistent with dimer
formation in pure acid. The monohydrate, sometimes called acetous acid, was formerly the
main article of commerce. Data on solidification points of aqueous acetic acid mixtures have
been tabulated and the eutectic formation has been sought for some time. The eutectic can be
decomposed through adding a substance to form a compound with acetic acid.
For example, Urea or Potassium acetate. Glacial acetic acid can then be distilled. The
densities of acetic acid-water mixtures at 15C are given in table 1.5.

Table 1.5. Density Of Acetic Acid

Acetic Acid Density

1 1.007

5 1.0067

10 1.10142

15 1.0214

20 1.0284

30 1.0412

40 1.0523

50 1.0615

60 1.0685

70 1.0733

80 1.0748

90 1.0713

23
 95 1.0660

100 1.0550

A summary of physical properties of glacial acetic acid is given in Table 1.6.

Table 1.6. Properties Of Glacial Acetic Acid

Property Value

Freezing point 16.635

Boiling point 117.87

Density 1.0495

Refractive index 1.36965

Heat of vaporization 394.5

Specific heat 5.029

Critical temperature 529.71

Critical pressure 4.53

Enthalpy of formation for liquid -484.50

For Gas -432.25

Normal enthalpy, J for liquid 159.8

For Gas 282.5

Liquid viscosity at 20C 11.83

Liquid viscosity at 40 C 8.18

Surface tension 27.75

Flammability limits 4.0 to 16

Auto-Ignition temperature 465

24
CHEMICAL PROPERTIES:
 Decomposition Reactions: Minute traces of acetic anhydride are formed when very
dry acetic acid is distilled. Without a catalyst, equilibrium is reached after about 7h of
boiling, but a trace of acid catalyst produces equilibrium in 20 minutes. At
equilibrium, about 4.2 mole of anhydride is present per liter of acetic acid, even at
temperature as low as 80C . Thermolysis of acetic acid occurs at 442C and
101.325kPa (1 atm), leading by parallel pathways to methane and carbon dioxide and
to ketene and water. Both reactions have great industrial significance.

Single pulse, shock tube decomposition of acetic acid in argon involves the same pair
of homogeneous, molecular first-oder reactions as thermolysis.

Platinum on graphite catalyzes the decomposition at 500-800K at low pressures.

Ketene, methane, carbon dioxide and a variety of minor products are obtained.
Photochemical decomposition yields methane and carbon dioxide and a number of
free radicals which have complicated pathways. Electron impact and gamma rays
appear to generate these products. Electron cyclotron resonance plasma made from
acetic acid deposits a diamond film on suitable surfaces. The film having a
polycrystalline structure, is a useful electrical insulator and widespread industrial
exploitation of diamond film appears to be on the horizon.

Acid-Base Chemistry: Acetic acid dissociates in water, pKa=4.76 at 25C. It is a mild

acid which can be used for analysis of bases too weak to detect in water. It readily
neutralizes the ordinary hydroxides of alkali metals and the alkaline earths to form the
corresponding acetates. When the crude material pyroligneous acid is neutralized with
limestone or magnesia the commercial acetate of lime or acetate of magnesia is
obtained. Acetic acid accepts protons only from the strongest acids such as nitric acid
and sulfuric acid. Other acids exhibit very powerful, super acid properties in acetic
acid solutions and are thus useful catalyst for esterification of olefins and alcohols.
Nitration’s conducted in acetic acid solvent are affected because of the formation of
the nitronium ion, NO2+. Hexamethylenetetramine may be nitrated in acetic acid
solvent to yield the explosive cyclotrimethylenetrinitramine , also known as cyclonit
or RDX.

 Acetylation Reactions : Alcohols may be acetylated without catalysts by using a

large excess of acetic acid .

The reaction rate is increased by using an entraining agent such as hexane, benzene or
cyclohexane, depending on the reactant alcohol to remove the water formed. The
concenteration of water in the reaction medium can be measured, either by means of
Karl-Fischer reagent, or automatically by specific conductance and used as control of
rate. The specific electrical conductance of acetic acid containing small amounts of
water is given in Table 1.7.

25
 Table 1.7. Specific Conductance Of Aquatic Acetic Acid

Acetic Acid, wt% Specific Conductance

100 0.060

99.9515 0.065

99.746 0.103

99.320 0.261

98.84 0.531

97.66 2.19

96.68 5.45

94.82 20.1

92.50 59.9

90.75 111

82.30 688

Nearly all commercial acetylation’s are realized using acetic catalysts. Catalytic acetylation
of alcohols can be carried out using mineral acids.
For example, Perchloric acid, phosphoric acid, sulfuric acid, benzenesulfonic acid or
methanesulfonic acid, as the catalyst. Certain acid reacting ion exchange resins may also be
used but these tend to decompose in acetic acid. Mordenite, a decationized Y-zeolite, is a
useful acetylation catalyst and aluminium chloride, Al2Cl6, catalyzes n-butanol acetylation.
Olefins and anhydrous acetic acid to give esters, usually, a precursor of vinyl acetate, has
long being known, but the condensation of formaldehyde and acetic acid vapors to furnish
acrylic acid and thus are not likely to be further developed. Vapor phase methanol –methyl
acetate oxidation using simultaneously condensation to yield methyl acrylate is still being
developed. A vanadium-titania phosphate catalyst is employed in that process.
Commercial production of acetic acid has been revolutionized in the decade 1978-1988.
Butane- naphtha liquid phase catalytic oxidation has declined precipitously as methanol or
methyl acetate carbonylation has become the technology of choice in the world of market.
By-product acetic acid recovery in other hydrocarbon oxidation.
For example, in xylene oxidation to terephthalic acid and propylene conversion to acrylic
acid, has also grown. Production from synthesis gas is increasing and development of
alternative raw materials in under serious consideration following widespread dislocations in
the cost of raw material.

26
Ethanol fermentation is still used in vinegar production. Research on fermentative routes to
glacial acetic acid is also being pursued. Thermophilic, anaerobic microbial fermentations of
carbohydrates can be realized at high rates, if practical schemes can be developed for
removing acetic acid as fast as it is formed. Under usual conditions, about 5% acid brings the
anaerobic reaction to a halt, but continuous separation produces high yields at high CO2 is
another possible route to acetic acid.
Currently, almost all acetic acid produced commercially comes from acetaldehyde oxidation,
methanol or methyl acetate carbonylation or light hydrocarbon liquid –phase oxidation.
Comparatively, small amounts are generated by butane liquid phase oxidation, direct ethanol
oxidation and synthesis gas. Large amounts of acetic acid are recycled industrially in the
production of cellulose acetate, polyvinyl alcohol and aspirin and in board array of other
proprietary processes.
 Acetaldehyde Oxidation: Ethanol is easily dehydrogenated oxidatively to
acetaldehyde using silver, brass, or bronze catalysts. Acetaldehyde can then be
oxidized in the liquid phase in the presence of cobalt or manganese salts to yield
acetic acid. Peracetic acid formation is prevented by transition metal catalysts. Most
transition metal salts decomposes any peroxides that form but manganese is uniquely
effective.

27