Assignment 1

Carboxylic

Subject

UEMK 1013 Chemistry For Engineering

Course

Bachelor of Engineering (Hons) Chemical Engineering

Name of lecturer

Dr. Tee Shiau Foon

Name of Student

Student ID No

Year and Semester

CHOI YU HUI

1402693

Y1S2

HENG ZENG WEI

1402740

Y1S2

CONTRIBUTION:
1) Chemical Reaction (HENG ZENG WEI)
2) Industrial process being investigated (CHOI YU HUI)
3) Details on the specific operation/ process involved (CHOI YU HUI)
4) The uses and importance in term social economic value (HENG ZENG WEI)
5) References (CHOI YU HUI, HENG ZENG WEI)
WORDS : 1189 approximately

Carboxylic acid,whether water soluble or not are readily deprotonated by strong

bases(metal oxides,metal hydroxides,ammonia)to form carboxylate salts due to their

enhanced acidity.Direct reaction of reactive metals with carboxylic acids give salts and
hydrogen gas.The presence of carboxyl group can be tested when hydrogen gas is
released.Carboxylic acids react with sodium bicarbonate and sodium carbonate to form
water-soluble sodium salts and carbonic acid.This weaker acid then decomposes to form
carbon dioxide gas and water.

Basically,there is three ways to convert carboxylic acids to amides.The direct

conversion of a carboxylic acid with an amine is difficult because the basic amine would
deprotonate the acidic carboxyl group into unreactive ammonium carboxylate salts which
prevents the further reaction.However,amide can be formed if the ammonium carboxylate
salt is heated to a temperature above 100 0C to split out the water.The reaction is
complete when ammonium salt is dehydrated and amide
isformed.Secondly,dicylohexylcarbodiimide (DCC) is used as an activating reagent to
replace -OH with a better leaving group. DCC will activate the carbonyl group so that it
can displaced by amine during nucleophillic substitution.Lastly,conversion is more
easier if carboxylic acid is converted to more reactive acyl chloride first.

Acid chlorides can be prepared through the reaction of carboxylic acids with strong
acid catalyst such as thionyl chloride(SOCl2),phosphorus trichloride(PCl3) or phosphorus
pentachloride(PCl5)to enhance the reactivity of carboxylic acid.During nucleophillic acyl
substitution, the -OH poor leaving group is first protonated and converted to
a chlorosulfite intermediate which make it a better leaving group.It then reacts with a
nucleophilic chloride anion to give acyl chloride.

Carboxylic acids can be converted to 10alcohols with aldehyde as an intermediate

using powerful reducing agent Lithium aluminum hydride (LiAlH4).Reduction of a
carboxyl group is carried out in diethyl ether.The initial product(aluminum alkoxide)is
converted to 10alcohol,lithium and aluminum hydroxides after treated with
water.Filtration and evaporation of the ether solvent yields the primary alcohol.

Fischer esterification is a conversion of carboxylic acid to ester by heating it with

alcohol in the presence of a strong acid catalyst (H2SO4) to protonate the carbonyl group
and activates it towards nucleophillic attack.This acid-catalyzed nucleophilic acyl

substitution is reversible and at equilibrium.Equilibrium can be forced to the right by

using excess alcohol or remove water from reaction mixture to yield more ester.

Diazomethane(CH2N2)in ether solution reacts with carboxylic acid to form methyl

esters and nitrogen gas quantitatively.Transfer of acid proton happens and gives a
methyldiazonium salt.

Carboxylic acid reacts with 2 equivalents of an organolithium reagent to form ketone

in alkylation reaction. Acid is deprotonated by the first equvailent of the organolithium
reagent.The second equivalent adds to the carbonyl to give a stable dianion.

Carboxylic acid can be brominated in the alpha position by bromine and PBr3 as
catalyst in Hell-Volhard-Zelinskii reaction.It depends on the enol type character of the
carbonyl compound.The final product formed is an a-bromocarboxylic acid and hydrogen
bromide.

-ketoacids is an exception carboxylic acid that undergoes decarboxylation at

moderate heat.The immediate products are an enol and loss of CO2 from a carboxyl
group.
.

The application of carboxylic acid in industry had impressed in this modern

industrial age.The acetic acid is widely used in the food industry and the industrial
process of production of vinegar is being investigated.Vinegar is used as flavouring and
preservative whereas its vital element is acetic acid.The others primary raw materials
used are Acetobater(an aerobic bacterial),industrial starch,alcohol,yeast,oxygen and fruit
as flavouring agents.The initial process in the manufacturing of vinegar is the alcohol
fermentation from food containing carbohydrate()anaerobically by yeast to produce
alcohol.The alcohol is being processed through pasteurisation,filtration,dilution to control
its concentration.

The alcohol is then oxidised by Acetobacter to generate acetic acid through oxidation in
dark condition and finally the process is follow by ageing process.The ageing process is
to prevent the destruction of acid by acetic bacteria.

In the food industry,there are three conventianal methods to produce vinegar which is
Orleans method,Generator method and Submerged fermentation method.As Orleans
method is time consuming,Generator method is considered as commercial method and
universally utilised in industry.Generally,the product of Generator method is distilled and
industrial vinegar.For generator method, the generator is dominantly consist of a upright

tank with beech wood shaving inside,mash product inlet at the top,heat exchanger,feed
line,pump,cooling coils,air inlet at the bottom which allows the air to suck in and flow
through generator for oxidation process by bacteria whereas an air outlet lovated at the
upper part.The Acetobaters are allowed to grow in shaving to oxidise alcohol.The alcohol
solution drips down to the bottom through the shaving by having the tank fixed with
devices.
Through Generator method,the Acetobaters are introduced into the shaving,a noncompacting material to grow to form a thick sludge coating.The alcohol is prepared from
alcoholic fermentation and allows it to flow from the top thoughout the fillings.The
oxygen is sucked into the tank through the air puzzles at the side and bottom with the aid
of air compressor by compressing air into the holes.The concentration of the oxygen
determines the rate of the reaction.After a few days or weeks, the alcohol oxidation
occurs and alcohol is completely converted into vinegar by reaching the bottom of the
tank.The Acetobaters oxidised the alcohol at highest rate at 30C.The vinegar containing
high concentration acetic acid(14%) is produced and 2/3of vinegar leave the bottom tank
to the storage.Fresh alcohol solution is added into the tank when initial
temperature(21.1C)is reached.The vinegar is distilled with water by mixing with the
diluted liquid in the boiler and boils the mixture until the its boiling point.A The liquid is
vaporised and condensed in a condenser.A lower ecetic acid content(5%-6%) vinegar is
obtained.The process is repeated until lowest acetitation.The maximum rate operation
temparature of generator is 30-32C.The generator must be operated under control to
prevent over oxidation by controlling oxygen supply and prevent the generator exceed
temperature range by checking the thermometer of the tank as the production of vinegar
liberates heat.

Carboxylic acids are important raw material needed in production of

pharmaceuticals, food additives and preservative,rubber,plastics,soaps,perfumes and
animal feed.The global market for carboxylic acids escalates due to the increasing
demand for acids and their derivatives in wide scope of industry application.The
carboxylic acids market are further subdivided according to the manufacture products.For
instance, it can be segmented into formic acid, isobutyric acid,valeric acids,acetic acid
and etc.Based on the report, about US$ 12.14 Bn was valued for global market in 2014.It
is predicted to expand at a CAGR of 4.9% between 2015 and 2023 and will eventually
reach US$ 18.49 Bn by 2023. In terms of volume, global information states that 17.82
million tons of carboxylic acid is accounts for the use in industry where U.S. is the
dominant consumer in North America in 2014. High demand of carboxylic acid for drug
formulation in North America is essential due to the growth in elderly
population.Moreover, formic acid, propionic acid, and butyric acid which mainly used in
the animal feed industry drives the high demand for carboxylic acid in Europe market

such as Germany, U.K, France and Italy. China as one of the worlds major producer and
consumer also contribute to the carboxylic market in food ,beverages and textile industry.
REFERENCE
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Available at:
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Kosherconsumer.org, (2015). KosherConsumer.org- Articles. [online] Available at:
http://www.kosherconsumer.org/vinegar.htm [Accessed 19 Nov. 2015].
Emire, S. (2012). Vinegar Production Technology An Overview. [online]
ResearchGate. Available at:
https://www.researchgate.net/publication/280722745_Vinegar_Production_Technology__
An_Overview [Accessed 19 Nov. 2015].
Madehow.com, (2015). How vinegar is made - making, history, used, product, machine,
Raw Materials, Design. [online] Available at: http://www.madehow.com/Volume7/Vinegar.html [Accessed 19 Nov. 2015].
ltd, R. (2015). Carboxylic Acids Market for Food & Beverages, Animal Feed,
Pharmaceuticals, Personal Care & Cosmetics, Consumer Goods, Lubricants, and Other
End-users - Global Industry Analysis, Size, Share, Growth, Trends and Forecast 2015 2023. [online] Researchandmarkets.com. Available at:
http://www.researchandmarkets.com/research/pf6fw7/carboxylic_acids [Accessed 19
Nov. 2015].
Denniston, K. (2010). General, Organic and Biochemistry. London: McGraw Hill Higher
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McMurry, J. (2012). Quimica organica. Mexico: Cengage Learning