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Monday, July 1, 2019

Preservative

From Wikipedia, the free encyclopedia

A preservative is a substance or a chemical that is added to products such as food, beverages, pharmaceutical drugs, paints, biological samples, cosmetics, wood, and many other products to prevent decomposition by microbial growth or by undesirable chemical changes. In general, preservation is implemented in two modes, chemical and physical. Chemical preservation entails adding chemical compounds to the product. Physical preservation entails processes such as refrigeration or drying. Preservative food additives reduce the risk of foodborne infections, decrease microbial spoilage, and preserve fresh attributes and nutritional quality. Some physical techniques for food preservation include dehydration, UV-C radiation, freeze-drying, and refrigeration. Chemical preservation and physical preservation techniques are sometimes combined.

Antimicrobial preservatives

Antimicrobial preservatives prevent degradation by bacteria. This method is the most traditional and ancient type of preserving—ancient methods such as pickling and adding honey prevent microorganism growth by modifying the pH level. The most commonly used antimicrobial preservative is lactic acid. Common antimicrobial preservatives are presented in the table. Nitrates and nitrites are also antimicrobial. The detailed mechanism of these chemical compounds range from inhibiting growth of the bacteria to the inhibition of specific enzymes. Water-based home and personal care products use broad-spectrum preservatives, such as isothiazolinones and formaldehyde releasers, which may cause sensitization, allergic skin reactions, and toxicity to aquatic life.

E number chemical compound comment
E200 – E203 sorbic acid, sodium sorbate and sorbates common for cheese, wine, baked goods, personal care products
E210 – E213 benzoic acid, sodium benzoate and benzoates used in acidic foods such as jams, salad dressing, juices, pickles, carbonated drinks, soy sauce
E214 – E219 hydroxybenzoate and derivatives, "parabens" stable at a broad pH range, personal care products
E220 – E227 sulfur dioxide and sulfites common for fruits, wine
E249 – E250 nitrite used in meats to prevent botulism toxin
E251 – E252 nitrate used in meats
E270 lactic acid -
E280 – E283 propionic acid and sodium propionate baked goods
n/a isothiazolinones (MIT, CMIT, BIT) home and personal care products, paints/coatings
n/a formaldehyde releasers (DMDM hydantoin) home and personal care products

Antioxidants

The free radical pathway for the first phase of the oxidative rancidification of fats. This process is slowed by antioxidants.
 
The oxidation process spoils most food, especially those with a high fat content. Fats quickly turn rancid when exposed to oxygen. Antioxidants prevent or inhibit the oxidation process. The most common antioxidant additives are ascorbic acid (vitamin C) and ascorbates. Thus, antioxidants are commonly added to oils, cheese, and chips. Other antioxidants include the phenol derivatives BHA, BHT, TBHQ and propyl gallate. These agents suppress the formation of hydroperoxides. Other preservatives include ethanol and methylchloroisothiazolinone

E number chemical compound comment
E300-304 ascorbic acid, sodium ascorbate cheese, chips
E321 butylated hydroxytoluene, butylated hydroxyanisole also used in food packaging
E310-312 gallic acid and sodium gallate oxygen scavenger
E220 – E227 sulfur dioxide and sulfites beverages, wine
E306 – E309 tocopherols vitamin E activity

A variety of agents are added to sequester (deactivate) metal ions that otherwise catalyze the oxidation of fats. Common sequestering agents are disodium EDTA, citric acid (and citrates), tartaric acid, and lecithin.

Nonsynthetic compounds for food preservation

Citric and ascorbic acids target enzymes that degrade fruits and vegetables, e.g., mono/polyphenol oxidase which turns surfaces of cut apples and potatoes brown. Ascorbic acid and tocopherol, which are vitamins, are common preservatives. Smoking entails exposing food to a variety of phenols, which are antioxidants. Natural preservatives include rosemary and oregano extract, hops, salt, sugar, vinegar, alcohol, diatomaceous earth and castor oil

Traditional preservatives, such as sodium benzoate have raised health concerns in the past. Benzoate was shown in a study to cause hypersensitivity in some asthma sufferers. This has caused reexamination of natural preservatives which occur in vegetables.

History and methods

Preservatives have been used since prehistoric times. Smoked meat for example has phenols and other chemicals that delay spoilage. The preservation of foods has evolved greatly over the centuries and has been instrumental in increasing food security. The use of preservatives other than traditional oils, salts, paints, etc. in food began in the late 19th century, but was not widespread until the 20th century.

The use of food preservatives varies greatly depending on the country. Many developing countries that do not have strong governments to regulate food additives face either harmful levels of preservatives in foods or a complete avoidance of foods that are considered unnatural or foreign. These countries have also proven useful in case studies surrounding chemical preservatives, as they have been only recently introduced. In urban slums of highly populated countries, the knowledge about contents of food tends to be extremely low, despite consumption of these imported foods.

Drying

In ancient times the sun and wind naturally dried out foods. Middle Eastern and Oriental cultures started drying foods in 1,200 B.C. in the sun. The Romans used a lot of dry fruit. In the Middle Ages, people made “still houses” where fruits, vegetables, and herbs could dry out in climates that did not have strong sunlight. Sometimes fires were made to create heat to dry foods. Drying prevents yeasts and bread molds (Rhizopus) from growing by removing moisture so bacteria cannot grow.

Freezing

Cellars, caves, and cool streams were used for freezing. American estates had ice houses built to store ice and food on the ice. The icehouse was then converted to an “icebox”. The Icebox was converted in the 1800s to mechanical refrigeration. Clarence Birdseye found in the 1800s that freezing meats and vegetables at a low temperature made them taste better.

Fermenting

Fermenting was discovered when a few grains of barley were left in the rain and turned into beer. Microorganisms ferment the starch-derived sugars into alcohols. This is also how fruits are fermented into wine and cabbage into Kimchi or sauerkraut. Anthropologists believe that as early as 10,000 B.C people began to settle and grow barley. They began to make beer and believed that it was a gift from gods. It was used to preserve foods and to create more nutritious foods from less desirable ingredients. Vitamins are produced through fermentation by microorganisms making the end product more nutritious.

Pickling

Pickling occurs when foods are placed in a container with vinegar or another acid. It is thought that pickling came about when people used to place food in wine or beer to preserve it due to them having a low pH. Containers had to be stoneware or glass (vinegar will dissolve metal from pots). After the food was eaten, the pickling brine had other uses. Romans would make a concentrated pickle sauce called “garum”. It was very concentrated and the dish that it would be used in would only need a few drops to get the fish taste. Due to new foods arriving from Europe in the 16th century, food preservation increased. Ketchup originated from Europe as an oriental fish brine and when it made it to America, sugar was added. Pickling sauces were soon part of many recipes such as chutneys, relish, piccalilli, mustard, and ketchup when different spices were added to them.

Curing

The beginning of curing was done through dehydration. Salting was used by early cultures to help desiccate foods. Many different salts were used from different places such as rock salt, sea salt, spiced salt, etc.. People began to experiment and found in the 1800s that some salts gave meat an appealing red color instead of the grey that they were used to. During their experimenting in the 1920s they realized this mixture of salts were nitrates (saltpeter) that prevented Clostridium botulinum growth.

Jam and Jelly

Early cultures also used honey or sugar as a preservatives. Greece used a quince and honey mixture with a slight amount of drying and then tightly packed into jars. The Romans used the same technique but instead cooked the honey and quince mixture to make a solid texture. Indian and Oriental traders brought sugarcane to the northern climates where housewives were then able to make preservatives by heating fruit with the sugarcane.

Canning

Canning started in 1790 from a French confectioner, Nicolas Appert, when he found that by applying heat to food in sealed glass bottles, the food is free from spoilage. Appert’s ideas were tried by the French Navy with meat, vegetables, fruit, and milk in 1806. An Englishman, Peter Durand decided to use Appert’s method on tin cans in 1810. Even though Appert found a method that worked, he did not understand why it worked because many believed that the lack of air caused the preservation. In 1864 Louis Pasteur linked food spoilage/illness to microorganisms. Different foods are placed into jars or cans and heated to a microorganism and enzyme inactivating temperature. They are then cooled forming a vacuum seal which prevents microorganisms from contaminating the foods.

Public awareness of food preservation

Public awareness of food preservatives is uneven. Americans have a perception that food-borne illnesses happen more often in other countries. This may be true, but the occurrence of illnesses, hospitalizations, and deaths are still high. It is estimated by the Center for Disease Control (CDC) that each year there are 76 million illnesses, 325,000 hospitalizations, and 5,000 deaths linked to food-borne illness.

The increasing demand for ready-to-eat fresh food products has led to challenges for food distributors regarding the safety and quality of their foods. Artificial preservatives meet some of these challenges by preserving freshness for longer periods of time, but these preservatives can cause negative side-effects as well. Sodium nitrite is a preservative used in lunch meats, hams, sausages, hot dogs, and bacon to prevent botulism. It serves the important function of controlling the bacteria that cause botulism, but sodium nitrite can react with proteins, or during cooking at high heats, to form carcinogenic N-nitrosamines. It has also been linked to cancer in lab animals. The commonly used sodium benzoate has been found to extend the shelf life of bottled tomato paste to 40 weeks without loss of quality. However, it can form the carcinogen benzene when combined with vitamin C. Many food manufacturers have reformed their products to eliminate this combination, but a risk still exists. Consumption of sodium benzoate may also cause hyperactivity. For over 30 years, there has been a debate about whether or not preservatives and other food additives can cause hyperactivity. Studies have found that there may be increases in hyperactivity amongst children who consume artificial colorings and benzoate preservatives and who are already genetically predisposed to hyperactivity, but these studies were not entirely conclusive. Hyperactivity only increased moderately, and it was not determined if the preservatives, colorings, or a combination of the two were responsible for the increase.

Formic acid

From Wikipedia, the free encyclopedia

Formic acid
Skeletal structure of formic acid
3D model of formic acid
Formic acid 85 percent.jpg
Names
Preferred IUPAC name
Formic acid
Systematic IUPAC name
Methanoic acid
Other names
Carbonous acid; Formylic acid; Hydrogen carboxylic acid; Hydroxy(oxo)methane; Metacarbonoic acid; Oxocarbinic acid; Oxomethanol
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.000.527
EC Number 200-579-1
E number E236 (preservatives)
KEGG
PubChem CID
RTECS number LQ4900000
UNII
Properties
CH2O2
Molar mass 46.025 g·mol−1
Appearance Colorless fuming liquid
Odor Pungent, penetrating
Density 1.220 g/mL
Melting point 8.4 °C (47.1 °F; 281.5 K)
Boiling point 100.8 °C (213.4 °F; 373.9 K)
Miscible
Solubility Miscible with ether, acetone, ethyl acetate, glycerol, methanol, ethanol
Partially soluble in benzene, toluene, xylenes
log P −0.54
Vapor pressure 35 mmHg (20 °C)
Acidity (pKa) 3.77
Conjugate base Formate
-19.90·10−6 cm3/mol
1.3714 (20 °C)
Viscosity 1.57 cP at 268 °C
Structure
Planar
1.41 D (gas)
Thermochemistry
131.8 J/mol K
−425.0 kJ/mol
−254.6 kJ/mol
Pharmacology
QP53AG01 (WHO)
Hazards
Main hazards Corrosive; irritant;
sensitizer
Safety data sheet MSDS from JT Baker
R-phrases (outdated) R10 R35
S-phrases (outdated) (S1/2) S23 S26 S45
NFPA 704
Flammability code 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g., diesel fuelHealth code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gasReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calciumSpecial hazards (white): no codeNFPA 704 four-colored diamond
2
3
1
Flash point 69 °C (156 °F; 342 K)
601 °C (1,114 °F; 874 K)
Explosive limits 14–34%
18%–57% (90% solution)
Lethal dose or concentration (LD, LC):
LD50 (median dose)
700 mg/kg (mouse, oral), 1100 mg/kg (rat, oral), 4000 mg/kg (dog, oral)
7853 ppm (rat, 15 min)
3246 ppm (mouse, 15 min)
US health exposure limits (NIOSH):
PEL (Permissible)
TWA 5 ppm (9 mg/m3)
REL (Recommended)
TWA 5 ppm (9 mg/m3)
IDLH (Immediate danger)
30 ppm
Related compounds
Acetic acid
Propionic acid
Related compounds
Formaldehyde
Methanol
Supplementary data page
Refractive index (n),
Dielectric constantr), etc.
Thermodynamic
data
Phase behaviour
solid–liquid–gas
UV, IR, NMR, MS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Formic acid, systematically named methanoic acid, is the simplest carboxylic acid. The chemical formula is CH2O2. The chemical composition is HCOOH. It is an important intermediate in chemical synthesis and occurs naturally, most notably in some ants. The word "formic" comes from the Latin word for ant, formica, referring to its early isolation by the distillation of ant bodies. Esters, salts, and the anion derived from formic acid are called formates. Industrially, formic acid is produced from methanol.

Properties

Cyclic dimer of formic acid; dashed green lines represent hydrogen bonds
 
Formic acid is a colorless liquid having a pungent, penetrating odor at room temperature, not unlike the related acetic acid. It is miscible with water and most polar organic solvents, and is somewhat soluble in hydrocarbons. In hydrocarbons and in the vapor phase, it consists of hydrogen-bonded dimers rather than individual molecules. Owing to its tendency to hydrogen-bond, gaseous formic acid does not obey the ideal gas law. Solid formic acid, which can exist in either of two polymorphs, consists of an effectively endless network of hydrogen-bonded formic acid molecules. Formic acid also forms a low-boiling azeotrope with water (22.4%) and liquid formic acid also tends to supercool.

Natural occurrence

In nature, formic acid is found in most ants and in stingless bees of the genus Oxytrigona. The wood ants from the genus Formica can spray formic acid on their prey or to defend the nest. It is also found in the trichomes of stinging nettle (Urtica dioica). Formic acid is a naturally occurring component of the atmosphere primarily due to forest emissions.

Production

In 2009, the worldwide capacity for producing formic acid was 720,000 tonnes per year, roughly equally divided between Europe (350,000, mainly in Germany) and Asia (370,000, mainly in China) while production was below 1000 tonnes per year in all other continents. It is commercially available in solutions of various concentrations between 85 and 99 w/w %. As of 2009, the largest producers are BASF, Eastman Chemical Company, LC Industrial, and Feicheng Acid Chemicals, with the largest production facilities in Ludwigshafen (200,000 tonnes per year, BASF, Germany), Oulu (105,000, Eastman, Finland), Nakhon Pathom (n/a, LC Industrial), and Feicheng (100,000, Feicheng, China). 2010 prices ranged from around €650/tonne (equivalent to around $800/tonne) in Western Europe to $1250/tonne in the United States.

From methyl formate and formamide

When methanol and carbon monoxide are combined in the presence of a strong base, the result is methyl formate, according to the chemical equation:
CH3OH + CO → HCO2CH3
In industry, this reaction is performed in the liquid phase at elevated pressure. Typical reaction conditions are 80 °C and 40 atm. The most widely used base is sodium methoxide. Hydrolysis of the methyl formate produces formic acid:
HCO2CH3 + H2O → HCO2H + CH3OH
Efficient hydrolysis of methyl formate requires a large excess of water. Some routes proceed indirectly by first treating the methyl formate with ammonia to give formamide, which is then hydrolyzed with sulfuric acid:
HCO2CH3 + NH3 → HC(O)NH2 + CH3OH
2 HC(O)NH2 + 2H2O + H2SO4 → 2HCO2H + (NH4)2SO4
A disadvantage of this approach is the need to dispose of the ammonium sulfate byproduct. This problem has led some manufacturers to develop energy-efficient methods of separating formic acid from the excess water used in direct hydrolysis. In one of these processes, used by BASF, the formic acid is removed from the water by liquid-liquid extraction with an organic base.

Niche chemical routes

By-product of acetic acid production

A significant amount of formic acid is produced as a byproduct in the manufacture of other chemicals. At one time, acetic acid was produced on a large scale by oxidation of alkanes, by a process that cogenerates significant formic acid. This oxidative route to acetic acid is declining in importance, so that the aforementioned dedicated routes to formic acid have become more important.

Hydrogenation of carbon dioxide

The catalytic hydrogenation of CO2 to formic acid has long been studied. This reaction can be conducted homogeneously.

Oxidation of biomass

Formic acid can also be obtained by aqueous catalytic partial oxidation of wet biomass by the OxFA process. A Keggin-type polyoxometalate (H5PV2Mo10O40) is used as the homogeneous catalyst to convert sugars, wood, waste paper, or cyanobacteria to formic acid and CO2 as the sole byproduct. Yields of up to 53% formic acid can be achieved.

Laboratory methods

In the laboratory, formic acid can be obtained by heating oxalic acid in glycerol and extraction by steam distillation. Glycerol acts as a catalyst, as the reaction proceeds through a glyceryl oxalate intermediate. If the reaction mixture is heated to higher temperatures, allyl alcohol results. The net reaction is thus:
C2O4H2 → CO2H2 + CO2
Another illustrative method involves the reaction between lead formate and hydrogen sulfide, driven by the formation of lead sulfide.
Pb(HCOO)2 + H2S → 2HCOOH + PbS

Biosynthesis

Formic acid is named after ants which have high concentrations of the compound in their venom. In ants formic acid is derived from serine through a 5,10-Methenyltetrahydrofolate intermediate. The conjugate base of formic acid, formate, also occurs widely in nature. An assay for formic acid in body fluids, designed for determination of formate after methanol poisoning, is based on the reaction of formate with bacterial formate dehydrogenase.

Uses

A major use of formic acid is as a preservative and antibacterial agent in livestock feed. In Europe, it is applied on silage, including fresh hay, to promote the fermentation of lactic acid and to suppress the formation of butyric acid; it also allows fermentation to occur quickly, and at a lower temperature, reducing the loss of nutritional value. Formic acid arrests certain decay processes and causes the feed to retain its nutritive value longer, and so it is widely used to preserve winter feed for cattle. In the poultry industry, it is sometimes added to feed to kill E. coli bacteria. Use as preservative for silage and (other) animal feed constituted 30% of the global consumption in 2009.

Formic acid is also significantly used in the production of leather, including tanning (23% of the global consumption in 2009), and in dyeing and finishing textiles (9% of the global consumption in 2009) because of its acidic nature. Use as a coagulant in the production of rubber consumed 6% of the global production in 2009.

Formic acid is also used in place of mineral acids for various cleaning products, such as limescale remover and toilet bowl cleaner. Some formate esters are artificial flavorings and perfumes. 

Beekeepers use formic acid as a miticide against the tracheal mite (Acarapis woodi) and the Varroa destructor mite and Varroa jacobsoni mite.

Formic acid application has been reported to be an effective treatment for warts.

Formic acid can be used as a fuel (it can be used directly in formic acid fuel cells and indirectly in hydrogen fuel cells).

It is possible to use formic acid as an intermediary to produce isobutanol from CO2 using microbes

Formic acid is often used as a component of mobile phase in reversed-phase high-performance liquid chromatography (RP-HPLC) analysis and separation techniques for the separation of hydrophobic macromolecules, such as peptides, proteins and more complex structures including intact viruses. Especially when paired with mass spectrometry detection, formic acid offers several advantages over the more traditionally used phosphoric acid.

Chemical reactions

Formic acid is about ten times stronger than acetic acid. It is used as a volatile pH modifier in HPLC and capillary electrophoresis

Formic acid is a source for a formyl group for example in the formylation of methylaniline to N-methylformanilide in toluene.

In synthetic organic chemistry, formic acid is often used as a source of hydride ion. The Eschweiler-Clarke reaction and the Leuckart-Wallach reaction are examples of this application. It, or more commonly its azeotrope with triethylamine, is also used as a source of hydrogen in transfer hydrogenation
 
The Eschweiler–Clark reaction

As mentioned below, formic acid readily decomposes with concentrated sulfuric acid to form carbon monoxide.
CH2O2 + H2SO4 → H2SO4 + H2O + CO

Reactions

Formic acid shares most of the chemical properties of other carboxylic acids. Because of its high acidity, solutions in alcohols form esters spontaneously. Formic acid shares some of the reducing properties of aldehydes, reducing solutions of gold, silver, and platinum to the metals.

Decomposition

Heat and especially acids cause formic acid to decompose to carbon monoxide (CO) and water (dehydration). Treatment of formic acid with sulfuric acid is a convenient laboratory source of CO.

In the presence of platinum, it decomposes with a release of hydrogen and carbon dioxide.
CH2O2 → H2 + CO2
Soluble ruthenium catalysts are also effective. Carbon monoxide free hydrogen has been generated in a very wide pressure range (1–600 bar). Formic acid has been considered as a means of hydrogen storage. The co-product of this decomposition, carbon dioxide, can be rehydrogenated back to formic acid in a second step. Formic acid contains 53 g/L hydrogen at room temperature and atmospheric pressure, which is three and a half times as much as compressed hydrogen gas can attain at 350 bar pressure (14.7 g/L). Pure formic acid is a liquid with a flash point of +69 °C, much higher than that of gasoline (−40 °C) or ethanol (+13 °C).

Addition to alkenes

Formic acid is unique among the carboxylic acids in its ability to participate in addition reactions with alkenes. Formic acids and alkenes readily react to form formate esters. In the presence of certain acids, including sulfuric and hydrofluoric acids, however, a variant of the Koch reaction occurs instead, and formic acid adds to the alkene to produce a larger carboxylic acid.

Formic acid anhydride

An unstable formic anhydride, H(C=O)−O−(C=O)H, can be obtained by dehydration of formic acid with N,N′-dicyclohexylcarbodiimide in ether at low temperature.

History

Some alchemists and naturalists were aware that ant hills give off an acidic vapor as early as the 15th century. The first person to describe the isolation of this substance (by the distillation of large numbers of ants) was the English naturalist John Ray, in 1671. Ants secrete the formic acid for attack and defense purposes. Formic acid was first synthesized from hydrocyanic acid by the French chemist Joseph Gay-Lussac. In 1855, another French chemist, Marcellin Berthelot, developed a synthesis from carbon monoxide similar to the process used today. 

Formic acid was long considered a chemical compound of only minor interest in the chemical industry. In the late 1960s, however, significant quantities became available as a byproduct of acetic acid production. It now finds increasing use as a preservative and antibacterial in livestock feed.

Safety

Formic acid has low toxicity (hence its use as a food additive), with an LD50 of 1.8 g/kg (tested orally on mice). The concentrated acid is corrosive to the skin.

Formic acid is readily metabolized and eliminated by the body. Nonetheless, it has specific toxic effects; the formic acid and formaldehyde produced as metabolites of methanol are responsible for the optic nerve damage, causing blindness seen in methanol poisoning. Some chronic effects of formic acid exposure have been documented. Some experiments on bacterial species have demonstrated it to be a mutagen. Chronic exposure in humans may cause kidney damage. Another possible effect of chronic exposure is development of a skin allergy that manifests upon re-exposure to the chemical. 

Concentrated formic acid slowly decomposes to carbon monoxide and water, leading to pressure buildup in the containing vessel. For this reason, 98% formic acid is shipped in plastic bottles with self-venting caps.

The hazards of solutions of formic acid depend on the concentration. The following table lists the EU classification of formic acid solutions: 

Concentration (weight percent) Classification R-Phrases
2%–10% Irritant (Xi) R36/38
10%–90% Corrosive (C) R34
>90% Corrosive (C) R35

Formic acid in 85% concentration is flammable, and diluted formic acid is on the U.S. Food and Drug Administration list of food additives. The principal danger from formic acid is from skin or eye contact with the concentrated liquid or vapors. The U.S. OSHA Permissible Exposure Level (PEL) of formic acid vapor in the work environment is 5 parts per million parts of air (ppm).

Homework

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