Difference between revisions of "Hydrolysis" - New World Encyclopedia

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'''Hydrolysis''' is a [[chemical reaction]] during which one or more [[water (molecule)|water molecules]] are split into hydrogen and hydroxide ions which may go on to participate in further reactions.<ref>[http://goldbook.iupac.org/H02902.html Hydrolysis]. IUPAC Gold Book. Retrieved September 24, 2008.</ref><ref>[http://goldbook.iupac.org/S05762.html Solvolysis]. IUPAC Gold Book. Retrieved September 24, 2008.</ref> It is the type of reaction that is used to break down certain [[polymer]]s, especially those made by [[step-growth polymerization]]. Such [[polymer degradation]] is usually catalyzed by either [[acid]] or [[alkali]] attack, often increasing with their strength or [[pH]].
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'''Hydrolysis''' is a [[chemical reaction]] in which a [[chemical compound]] decomposes by reaction with [[water]]. The reacting [[water (molecule)|water molecules]] are split into hydrogen (H<sup>+</sup>) and hydroxide (OH<sup>&minus;</sup>) ions, which react with and break up (or "lyse") the other reacting compound.<ref>IUPAC Gold Book, [http://goldbook.iupac.org/H02902.html Hydrolysis]. Retrieved September 24, 2008.</ref> The term ''hydrolysis'' is also applied to the [[electrolysis]] of water (that is, breaking up of water molecules by an electric current) to produce [[hydrogen]] and [[oxygen]].
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The hydrolysis reaction breaks down a variety of [[polymer]]s, including [[protein]]s, [[carbohydrate]]s, [[fat]]s, and [[nucleic acid]]s. Such reactions may be [[catalyst|catalyzed]] by [[acid]]s, [[base (chemistry)|bases]], or [[enzyme]]s (classified as ''[[hydrolase]]s''). Such reactions regularly occur during the process of [[digestion]] of [[food]] in living systems. In addition, hydrolysis is said to occur when a [[salt]] reacts with water to produce new [[ion (physics)|ions]] or [[precipitate]]s.
  
Hydrolysis is distinct from a [[hydration reaction]], in which a hydrated molecule does not "lyse" (break into two new compounds). It should not be confused with [[hydrogenolysis]], a reaction of hydrogen.
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== Clarification of terminology ==
 
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The hydrolysis reaction is distinct from a ''[[hydration reaction]]'', in which water molecules attach to molecules of the other reacting compound without breaking up the latter compound. Also, hydrolysis should not be confused with ''[[hydrogenolysis]],'' a reaction of hydrogen.
"(Hydrolysis is) A chemical reaction in which water is used to break the bonds of certain substances. In biotechnology and living organisms, these substances are often polymers. In a hydrolysis reaction involving an ester link, such as that found between two amino acids in a protein, the products that result include one that receives the hydroxyl (OH) group from the water molecule, and another that becomes a carboxylic acid with the addition of the remaining proton (H+)."
 
 
 
"Hydrolysis reactions in living organisms are performed with the help of catalysis by a class of enzymes known as hydrolases. The biochemical reactions that break down polymers such as proteins (peptide bonds between amino acids), nucleotides, complex sugars and starch, and fats are catalyzed by this class of enzymes. Within this class, lipases, amylases and proteinases hydrolyze fats, sugars and proteins, respectively."
 
  
 
==Types==
 
==Types==
 +
There are various types of hydrolysis reactions, as noted below.
  
In [[organic chemistry]], hydrolysis can be considered as the reverse or opposite of [[condensation reaction|condensation]], a reaction in which two molecular fragments are joined for each water molecule produced. As hydrolysis may be a reversible reaction, condensation and hydrolysis can take place at the same time, with the position of equilibrium determining the amount of each product. A typical example is the hydrolysis of an ester to an acid and an alcohol.
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* In [[organic chemistry]], hydrolysis can be considered the reverse (or opposite) of [[condensation reaction|condensation]], a reaction in which two molecular fragments are joined for each water molecule produced. As hydrolysis may be a reversible reaction, condensation and hydrolysis can take place at the same time, with the position of equilibrium determining the amount of each product. A typical example is the hydrolysis of an ester to an acid and an alcohol.
  
:R<sup>1</sup>CO<sub>2</sub>R<sup>2</sup> + H<sub>2</sub>O {{unicode|&#8652;}} R<sup>1</sup>CO<sub>2</sub>H + R<sup>2</sup>OH
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::R<sup>1</sup>CO<sub>2</sub>R<sup>2</sup> + H<sub>2</sub>O {{unicode|&#8652;}} R<sup>1</sup>CO<sub>2</sub>H + R<sup>2</sup>OH
  
In [[inorganic chemistry]], the word is often applied to solutions of salts and the reactions by which they are converted to new ionic species or to precipitates (oxides, hydroxides, or salts). The addition of a molecule of water to a chemical compound, without forming any other products is usually known as [[hydration reaction|hydration]], rather than ''hydrolysis''.
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* In [[inorganic chemistry]], the word is often applied to solutions of salts and the reactions by which they are converted to new ionic species or to precipitates (oxides, hydroxides, or salts).
  
In [[biochemistry]], hydrolysis is considered the reverse or opposite of [[dehydration synthesis]]. In hydrolysis, a water molecule (H<sub>2</sub>O), is added, whereas in dehydration synthesis, a molecule of water is removed.
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* In [[biochemistry]], hydrolysis is considered the reverse or opposite of [[dehydration synthesis]]. In hydrolysis, a water molecule (H<sub>2</sub>O), is added, whereas in dehydration synthesis, a molecule of water is removed.
  
In [[electrochemistry]], hydrolysis can also refer to the [[electrolysis of water]]. In hydrolysis, a voltage is applied across an aqueous medium, which produces a current and breaks the water into its constituents, hydrogen and oxygen.
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* In [[electrochemistry]], hydrolysis can also refer to the [[electrolysis of water]]. In hydrolysis, a voltage is applied across an aqueous medium, which produces a current and breaks the water into its constituents, [[hydrogen]] and [[oxygen]].
  
In [[polymer chemistry]], hydrolysis of [[polymer]]s can occur during high-temperature processing such as [[injection moulding]] leading to chain degradation and loss of product integrity. Polymers most at risk include [[Polyethylene terephthalate|PET]], [[polycarbonate]], [[nylon]] and other polymers made by [[step-growth polymerization]]. Such materials must be dried prior to moulding.
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* In [[polymer chemistry]], hydrolysis of [[polymer]]s can occur during high-temperature processing such as [[injection moulding]] leading to chain degradation and loss of product integrity. Polymers most at risk include [[Polyethylene terephthalate|PET]], [[polycarbonate]], [[nylon]] and other polymers made by [[step-growth polymerization]]. Such materials must be dried prior to molding.
  
 
== Hydrolysis of amide links ==
 
== Hydrolysis of amide links ==
 
 
In the hydrolysis of an [[amide]] link into a [[carboxylic acid]] and an [[amine]] or [[ammonia]], the carboxylic acid has an hydroxyl group derived from a water molecule and the amine (or ammonia) gains the hydrogen ion.
 
In the hydrolysis of an [[amide]] link into a [[carboxylic acid]] and an [[amine]] or [[ammonia]], the carboxylic acid has an hydroxyl group derived from a water molecule and the amine (or ammonia) gains the hydrogen ion.
 
   
 
   
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A specific case of the hydrolysis of an amide link is the hydrolysis of [[peptide bond|peptides]] to smaller fragments or [[amino acid]]s.  
 
A specific case of the hydrolysis of an amide link is the hydrolysis of [[peptide bond|peptides]] to smaller fragments or [[amino acid]]s.  
  
Many [[polyamide]] polymers such as [[nylon 6,6]] are attacked and hydrolysed in the presence of strong acids. Such attack leads to [[depolymerization]] and nylon products fail by fracturing when exposed to even small amounts of acid. Other polymers made by [[step-growth polymerization]] are susceptible to similar [[polymer degradation]] reactions. The problem is known as [[stress corrosion cracking]].
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Many [[polyamide]] polymers such as [[nylon 6,6]] are attacked and hydrolyzed in the presence of strong acids. Such attack leads to [[depolymerization]] and nylon products fail by fracturing when exposed to even small amounts of acid. Other polymers made by [[step-growth polymerization]] are susceptible to similar [[polymer degradation]] reactions. The problem is known as [[stress corrosion cracking]].
  
 
== Hydrolysis of polysaccharides ==
 
== Hydrolysis of polysaccharides ==
[[image:Sucrose-inkscape.svg|thumb|Sucrose. The glycoside bond is represented by the cetral oxygen atom which holds the two monosaccharide units together]]
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[[image:Sucrose-inkscape.svg|thumb|Sucrose. The glycoside bond is represented by the central oxygen atom that holds the two monosaccharide units together.]]
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In a [[polysaccharide]] molecule, [[monosaccharide]] subunits are linked together by [[glycosidic bond]]s. This bond can be cleaved by hydrolysis to yield monosaccharides. The best known disaccharide is [[sucrose]] (table sugar). Hydrolysis of sucrose yields [[glucose]] and [[fructose]].
  
In a [[polysaccharide]] molecule, [[monosaccharide]] subunits are linked together by [[glycosidic bond]]s. This bond can be cleaved by hydrolysis to yield monosaccharides. The best known disaccharide is [[sucrose]] (table sugar). Hydrolysis of sucrose yields [[glucose]] and [[fructose]]. There are many [[enzymes]] which speed up the hydrolysis of polysaccharides. [[Invertase]] is used industrially to hydrolyze sucrose to so-called [[invert sugar]]. Invertase is an example of a [[glycoside hydrolase]] (glucosidase). [[Lactase]] is essential for digestive hydrolysis of [[lactose]] in milk. Deficiency of the enzyme in humans causes [[lactose intolerance]]. &beta;-[[amylase]] catalyzes the conversion of [[starch]] to [[maltose]]. Malt made from [[barley]] is used as a source of &beta;-amylase to break down starch into a form that can be used by yeast to produce [[beer]]. The hydrolysis of [[cellulose]] into glucose, known as ''saccharification'', is catalyzed by [[cellulase]]. Animals such as cows ([[ruminants]]) are able to digest cellulose because of the presence of parasitic bacteria which produce cellulases.
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There are many [[enzymes]] that speed up the hydrolysis of polysaccharides. [[Invertase]] is used industrially to hydrolyze sucrose to so-called [[invert sugar]]. Invertase is an example of a [[glycoside hydrolase]] (glucosidase). [[Lactase]] is essential for digestive hydrolysis of [[lactose]] in milk. Deficiency of the enzyme in humans causes [[lactose intolerance]]. &beta;-[[amylase]] catalyzes the conversion of [[starch]] to [[maltose]]. Malt made from [[barley]] is used as a source of &beta;-amylase to break down starch into a form that can be used by yeast to produce [[beer]]. The hydrolysis of [[cellulose]] into glucose, known as ''saccharification,'' is catalyzed by [[cellulase]]. Animals such as cows ([[ruminants]]) are able to digest cellulose because of the presence of parasitic bacteria that produce cellulases.
  
 
== Hydrolysis of metal aqua ions ==
 
== Hydrolysis of metal aqua ions ==
 
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Metal ions are [[Lewis acid]]s, and in aqueous solution they form "aqua ions," of the general formula M(H<sub>2</sub>O)<sub>n</sub><sup>m+</sup>.<ref>John Burgess, ''Metal Ions in Solution'' (Chichester: Ellis Horwood, 1978, ISBN 0470262931).</ref> The aqua ions are hydrolyzed, to a greater or lesser extent. The first hydrolysis step is given generically as
Metal ions are [[Lewis acid]]s, and in aqueous solution they form aqua ions, of the general formula M(H<sub>2</sub>O)<sub>n</sub><sup>m+</sup>.<ref>Burgess, John. 1978. ''Metal Ions in Solution.'' Chichester: Ellis Horwood. ISBN 0470262931.</ref><ref>Richens, David T. 1997. ''The Chemistry of Aqua Ions: Synthesis, Structure, and Reactivity : A Tour Through the Periodic Table of the Elements.'' Chichester: Wiley. ISBN 0471970581.</ref> The aqua ions are hydrolyzed, to a greater or lesser extent. The first hydrolysis step is given generically as
 
  
 
: M(H<sub>2</sub>O)<sub>n</sub><sup>m+</sup> + H<sub>2</sub>O {{unicode|&#8652;}} M(H<sub>2</sub>O)<sub>n-1</sub>(OH)<sup>(m-1)+</sup> + H<sub>3</sub>O<sup>+</sup>
 
: M(H<sub>2</sub>O)<sub>n</sub><sup>m+</sup> + H<sub>2</sub>O {{unicode|&#8652;}} M(H<sub>2</sub>O)<sub>n-1</sub>(OH)<sup>(m-1)+</sup> + H<sub>3</sub>O<sup>+</sup>
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Thus the aqua ion is behaving as an acid in terms of [[Brønsted-Lowry acid-base theory]]. This is easily explained by considering the [[inductive effect]] of the positively charged metal ion, which weakens the O-H bond of an attached water molecule, making the liberation of a proton relatively easy.  
 
Thus the aqua ion is behaving as an acid in terms of [[Brønsted-Lowry acid-base theory]]. This is easily explained by considering the [[inductive effect]] of the positively charged metal ion, which weakens the O-H bond of an attached water molecule, making the liberation of a proton relatively easy.  
  
The [[Acid dissociation constant |dissociation constant]], pK<sub>a</sub>, for this reaction is more or less linearly related to the charge-to-size ratio of the metal ion.<ref name="bm">Baes, Charles F., and Robert E. Mesmer. 1976. ''The Hydrolysis of Cations.'' New York: Wiley. ISBN 0471039853.</ref> Ions with low charges, such as Na<sup>+</sup> are very weak acids with almost imperceptible hydrolysis. Large divalent ions such as Ca<sup>2+</sup>, Zn<sup>2+</sup>, Sn<sup>2+</sup> and Pb<sup>2+</sup> have a pK<sub>a</sub> of 6 or more and would not normally be classed as acids, but small divalent ions such as Be<sup>2+</sup> are extensively hydrolyzed. Trivalent ions like Al<sup>3+</sup> and Fe<sup>3+</sup> are weak acids whose pK<sub>a</sub> is comparable to that of [[acetic acid]]. Solutions of salts such as BeCl<sub>2</sub> or Al(NO<sub>3</sub>)<sub>3</sub> in water are noticeably [[acidic]]; the hydrolysis can be [[le chatelier's principle|suppressed]] by adding an acid such as [[nitric acid]], making the solution more acidic.  
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The [[Acid dissociation constant |dissociation constant]], pK<sub>a</sub>, for this reaction is more or less linearly related to the charge-to-size ratio of the metal ion.<ref name="bm">Charles F. Baes and Robert E. Mesmer, ''The Hydrolysis of Cations'' (New York: Wiley, 1976, ISBN 0471039853).</ref> Ions with low charges, such as Na<sup>+</sup> are very weak acids with almost imperceptible hydrolysis. Large divalent ions such as Ca<sup>2+</sup>, Zn<sup>2+</sup>, Sn<sup>2+</sup> and Pb<sup>2+</sup> have a pK<sub>a</sub> of 6 or more and would not normally be classed as acids, but small divalent ions such as Be<sup>2+</sup> are extensively hydrolyzed. Trivalent ions like Al<sup>3+</sup> and Fe<sup>3+</sup> are weak acids whose pK<sub>a</sub> is comparable to that of [[acetic acid]]. Solutions of salts such as BeCl<sub>2</sub> or Al(NO<sub>3</sub>)<sub>3</sub> in water are noticeably [[acidic]]; the hydrolysis can be [[le chatelier's principle|suppressed]] by adding an acid such as [[nitric acid]], making the solution more acidic.  
  
Hydrolysis may proceed beyond the first step, often with the formation of polynuclear species.  
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Hydrolysis may proceed beyond the first step, often with the formation of polynuclear species.<ref name="bm"/> Some "exotic" species such as Sn<sub>3</sub>(OH)<sub>4</sub><sup>2+</sup><ref>N.N. Greenwood and A. Earnshaw, ''Chemistry of the Elements'' (Oxford: Butterworth-Heinemann, 2006).</ref> are well characterized. Hydrolysis tends to increase as [[pH]] rises leading, in many cases, to the precipitation of an hydroxide such as Al(OH)<sub>3</sub> or AlO(OH). These substances, the major constituents of [[bauxite]], are known as [[laterite]]s  and are formed by leaching from rocks of most of the ions other than aluminum and iron and subsequent hydrolysis of the remaining aluminum and iron.
<ref name="bm"/> Some "exotic" species such as Sn<sub>3</sub>(OH)<sub>4</sub><sup>2+</sup> <ref>Greenwood, N. N., and A. Earnshaw. 2006. ''Chemistry of the Elements.'' Oxford: Butterworth-Heinemann. p384.</ref> are well characterized. Hydrolysis tends to increase as [[pH]] rises leading, in many cases, to the precipitation of an hydroxide such as Al(OH)<sub>3</sub> or AlO(OH). These substances, the major constituents of [[bauxite]], are known as [[laterite]]s  and are formed by leaching from rocks of most of the ions other than aluminum and iron and subsequent hydrolysis of the remaining aluminum and iron.
 
  
 
Ions with a formal charge of four are extensively hydrolyzed and salts of Zr<sup>4+</sup>, for example,  can only be obtained from strongly acidic solutions. With oxidation states five and higher the concentration of the aqua ion in solution is negligible. In effect the aqua ion is a strong acid. For example, aqueous solutions of Cr(VI) contain CrO<sub>4</sub><sup>2-</sup>.  
 
Ions with a formal charge of four are extensively hydrolyzed and salts of Zr<sup>4+</sup>, for example,  can only be obtained from strongly acidic solutions. With oxidation states five and higher the concentration of the aqua ion in solution is negligible. In effect the aqua ion is a strong acid. For example, aqueous solutions of Cr(VI) contain CrO<sub>4</sub><sup>2-</sup>.  
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== Irreversibility of hydrolysis under physiological conditions ==
 
== Irreversibility of hydrolysis under physiological conditions ==
 
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Under physiological conditions (i.e. in dilute aqueous solution), a hydrolytic cleavage reaction, where the concentration of a metabolic precursor is low (on the order of 10<sup>-3</sup> to 10<sup>-6</sup> molar) and the reaction is catalyzed by an enzyme, is essentially [[thermodynamics|thermodynamically]] irreversible. This theme of physiological irreversibility of hydrolysis is used consistently in metabolic pathways, since many biological processes are driven by the cleavage of [[anhydride|anhydrous]] [[pyrophosphate]] bonds.
Under physiological conditions (i.e. in dilute aqueous solution), a hydrolytic cleavage reaction, where the concentration of a metabolic precursor is low (on the order of 10<sup>-3</sup> to 10<sup>-6</sup> molar), is essentially [[thermodynamics|thermodynamically]] irreversible. To give an example:
 
 
 
: A + H<sub>2</sub>O → X + Y
 
 
 
: <math>K_d = \frac{\left[X\right] \left[Y\right]} {\left[H_2O\right] \left[A\right]}</math>
 
 
 
Assuming that ''x'' is the final concentration of products, and that ''C'' is the initial concentration of A, and W = [H<sub>2</sub>O] = 55.5 molar, then ''x'' can be calculated with the equation:
 
 
 
: <math>\frac{x \times x}{W\left(C - x\right)} = K_d</math>
 
 
 
let K<sub>d</sub>×W = k:
 
 
 
then <math> x = \frac {-k + \sqrt {k^2 + 4kC} } {2}. </math>
 
 
 
For a value of C = 0.001 molar, and k = 1 molar, ''x''/C &gt; 0.999. Less than 0.1% of the original reactant would be present once the reaction is complete.
 
 
 
This theme of physiological irreversibility of hydrolysis is used consistently in metabolic pathways, since many biological processes are driven by the cleavage of [[anhydride|anhydrous]] [[pyrophosphate]] bonds.
 
  
 
== See also ==
 
== See also ==
  
* [[Adenosine triphosphate]]
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* [[Enzyme]]
* [[Dehydration synthesis]]
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* [[Polymer]]
* [[Polymer degradation]]
 
* [[Solvolysis]]
 
 
* [[Water]]
 
* [[Water]]
  
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== References ==
 
== References ==
 
 
* Baes, Charles F., and Robert E. Mesmer. 1976. ''The Hydrolysis of Cations.'' New York: Wiley. ISBN 0471039853.
 
* Baes, Charles F., and Robert E. Mesmer. 1976. ''The Hydrolysis of Cations.'' New York: Wiley. ISBN 0471039853.
 
 
* Burgess, John. 1978. ''Metal Ions in Solution.'' Chichester: Ellis Horwood. ISBN 0470262931.
 
* Burgess, John. 1978. ''Metal Ions in Solution.'' Chichester: Ellis Horwood. ISBN 0470262931.
 
 
* Frey, Perry A., and Adrian D. Hegeman. 2007. ''Enzymatic Reaction Mechanisms.'' Oxford: Oxford University Press. ISBN 978-0195122589.
 
* Frey, Perry A., and Adrian D. Hegeman. 2007. ''Enzymatic Reaction Mechanisms.'' Oxford: Oxford University Press. ISBN 978-0195122589.
 
+
* Richens, David T. 1997. ''The Chemistry of Aqua Ions: Synthesis, Structure, and Reactivity: A Tour Through the Periodic Table of the Elements.'' Chichester: Wiley. ISBN 0471970581.
* Richens, David T. 1997. ''The Chemistry of Aqua Ions: Synthesis, Structure, and Reactivity : A Tour Through the Periodic Table of the Elements.'' Chichester: Wiley. ISBN 0471970581.
 
 
 
 
* Silverman, Richard B. 2002. ''The Organic Chemistry of Enzyme-Catalyzed Reactions.'' San Diego: Academic Press. ISBN 0126437319.
 
* Silverman, Richard B. 2002. ''The Organic Chemistry of Enzyme-Catalyzed Reactions.'' San Diego: Academic Press. ISBN 0126437319.
 
 
* Testa, Bernard, and Joachim M. Mayer. 2003. ''Hydrolysis in Drug and Prodrug Metabolism: Chemistry, Biochemistry, and Enzymology.'' Weinheim: Wiley-VCH. ISBN 390639025X.
 
* Testa, Bernard, and Joachim M. Mayer. 2003. ''Hydrolysis in Drug and Prodrug Metabolism: Chemistry, Biochemistry, and Enzymology.'' Weinheim: Wiley-VCH. ISBN 390639025X.
  
 
==External links==
 
==External links==
 
+
All links retrieved January 22, 2018.
* [http://www.avogadro.co.uk/organic/hydrolysis/hydrolysis.htm Hydrolysis of Organic Compounds]. Retrieved September 24, 2008.
+
* [https://www.thebalance.com/what-is-hydrolysis-375589 An Explanation of the Process Hydrolysis]. ''the balance''.  
 
 
* [http://biotech.about.com/od/glossary/g/hydrolysis.htm Hydrolysis]. About.com. Retrieved September 24, 2008.
 
  
 
[[Category:Physical sciences]]
 
[[Category:Physical sciences]]

Latest revision as of 20:06, 22 January 2018

Hydrolysis is a chemical reaction in which a chemical compound decomposes by reaction with water. The reacting water molecules are split into hydrogen (H+) and hydroxide (OH) ions, which react with and break up (or "lyse") the other reacting compound.[1] The term hydrolysis is also applied to the electrolysis of water (that is, breaking up of water molecules by an electric current) to produce hydrogen and oxygen.

The hydrolysis reaction breaks down a variety of polymers, including proteins, carbohydrates, fats, and nucleic acids. Such reactions may be catalyzed by acids, bases, or enzymes (classified as hydrolases). Such reactions regularly occur during the process of digestion of food in living systems. In addition, hydrolysis is said to occur when a salt reacts with water to produce new ions or precipitates.

Clarification of terminology

The hydrolysis reaction is distinct from a hydration reaction, in which water molecules attach to molecules of the other reacting compound without breaking up the latter compound. Also, hydrolysis should not be confused with hydrogenolysis, a reaction of hydrogen.

Types

There are various types of hydrolysis reactions, as noted below.

  • In organic chemistry, hydrolysis can be considered the reverse (or opposite) of condensation, a reaction in which two molecular fragments are joined for each water molecule produced. As hydrolysis may be a reversible reaction, condensation and hydrolysis can take place at the same time, with the position of equilibrium determining the amount of each product. A typical example is the hydrolysis of an ester to an acid and an alcohol.
R1CO2R2 + H2O R1CO2H + R2OH
  • In inorganic chemistry, the word is often applied to solutions of salts and the reactions by which they are converted to new ionic species or to precipitates (oxides, hydroxides, or salts).
  • In biochemistry, hydrolysis is considered the reverse or opposite of dehydration synthesis. In hydrolysis, a water molecule (H2O), is added, whereas in dehydration synthesis, a molecule of water is removed.
  • In electrochemistry, hydrolysis can also refer to the electrolysis of water. In hydrolysis, a voltage is applied across an aqueous medium, which produces a current and breaks the water into its constituents, hydrogen and oxygen.
  • In polymer chemistry, hydrolysis of polymers can occur during high-temperature processing such as injection moulding leading to chain degradation and loss of product integrity. Polymers most at risk include PET, polycarbonate, nylon and other polymers made by step-growth polymerization. Such materials must be dried prior to molding.

Hydrolysis of amide links

In the hydrolysis of an amide link into a carboxylic acid and an amine or ammonia, the carboxylic acid has an hydroxyl group derived from a water molecule and the amine (or ammonia) gains the hydrogen ion.

Amide hydrolysis.png

A specific case of the hydrolysis of an amide link is the hydrolysis of peptides to smaller fragments or amino acids.

Many polyamide polymers such as nylon 6,6 are attacked and hydrolyzed in the presence of strong acids. Such attack leads to depolymerization and nylon products fail by fracturing when exposed to even small amounts of acid. Other polymers made by step-growth polymerization are susceptible to similar polymer degradation reactions. The problem is known as stress corrosion cracking.

Hydrolysis of polysaccharides

Sucrose. The glycoside bond is represented by the central oxygen atom that holds the two monosaccharide units together.

In a polysaccharide molecule, monosaccharide subunits are linked together by glycosidic bonds. This bond can be cleaved by hydrolysis to yield monosaccharides. The best known disaccharide is sucrose (table sugar). Hydrolysis of sucrose yields glucose and fructose.

There are many enzymes that speed up the hydrolysis of polysaccharides. Invertase is used industrially to hydrolyze sucrose to so-called invert sugar. Invertase is an example of a glycoside hydrolase (glucosidase). Lactase is essential for digestive hydrolysis of lactose in milk. Deficiency of the enzyme in humans causes lactose intolerance. β-amylase catalyzes the conversion of starch to maltose. Malt made from barley is used as a source of β-amylase to break down starch into a form that can be used by yeast to produce beer. The hydrolysis of cellulose into glucose, known as saccharification, is catalyzed by cellulase. Animals such as cows (ruminants) are able to digest cellulose because of the presence of parasitic bacteria that produce cellulases.

Hydrolysis of metal aqua ions

Metal ions are Lewis acids, and in aqueous solution they form "aqua ions," of the general formula M(H2O)nm+.[2] The aqua ions are hydrolyzed, to a greater or lesser extent. The first hydrolysis step is given generically as

M(H2O)nm+ + H2O M(H2O)n-1(OH)(m-1)+ + H3O+

Thus the aqua ion is behaving as an acid in terms of Brønsted-Lowry acid-base theory. This is easily explained by considering the inductive effect of the positively charged metal ion, which weakens the O-H bond of an attached water molecule, making the liberation of a proton relatively easy.

The dissociation constant, pKa, for this reaction is more or less linearly related to the charge-to-size ratio of the metal ion.[3] Ions with low charges, such as Na+ are very weak acids with almost imperceptible hydrolysis. Large divalent ions such as Ca2+, Zn2+, Sn2+ and Pb2+ have a pKa of 6 or more and would not normally be classed as acids, but small divalent ions such as Be2+ are extensively hydrolyzed. Trivalent ions like Al3+ and Fe3+ are weak acids whose pKa is comparable to that of acetic acid. Solutions of salts such as BeCl2 or Al(NO3)3 in water are noticeably acidic; the hydrolysis can be suppressed by adding an acid such as nitric acid, making the solution more acidic.

Hydrolysis may proceed beyond the first step, often with the formation of polynuclear species.[3] Some "exotic" species such as Sn3(OH)42+[4] are well characterized. Hydrolysis tends to increase as pH rises leading, in many cases, to the precipitation of an hydroxide such as Al(OH)3 or AlO(OH). These substances, the major constituents of bauxite, are known as laterites and are formed by leaching from rocks of most of the ions other than aluminum and iron and subsequent hydrolysis of the remaining aluminum and iron.

Ions with a formal charge of four are extensively hydrolyzed and salts of Zr4+, for example, can only be obtained from strongly acidic solutions. With oxidation states five and higher the concentration of the aqua ion in solution is negligible. In effect the aqua ion is a strong acid. For example, aqueous solutions of Cr(VI) contain CrO42-.

Cr(H2O)6+ → CrO42- + 2 H2O + 8 H+

Note that reactions such as

2 CrO42- + H2O Cr2O72- + 2 OH-

are formally hydrolysis reactions as water molecules are split up yielding hydroxide ions. Such reactions are common among polyoxometalates.

Irreversibility of hydrolysis under physiological conditions

Under physiological conditions (i.e. in dilute aqueous solution), a hydrolytic cleavage reaction, where the concentration of a metabolic precursor is low (on the order of 10-3 to 10-6 molar) and the reaction is catalyzed by an enzyme, is essentially thermodynamically irreversible. This theme of physiological irreversibility of hydrolysis is used consistently in metabolic pathways, since many biological processes are driven by the cleavage of anhydrous pyrophosphate bonds.

See also

Notes

  1. IUPAC Gold Book, Hydrolysis. Retrieved September 24, 2008.
  2. John Burgess, Metal Ions in Solution (Chichester: Ellis Horwood, 1978, ISBN 0470262931).
  3. 3.0 3.1 Charles F. Baes and Robert E. Mesmer, The Hydrolysis of Cations (New York: Wiley, 1976, ISBN 0471039853).
  4. N.N. Greenwood and A. Earnshaw, Chemistry of the Elements (Oxford: Butterworth-Heinemann, 2006).

References
ISBN links support NWE through referral fees

  • Baes, Charles F., and Robert E. Mesmer. 1976. The Hydrolysis of Cations. New York: Wiley. ISBN 0471039853.
  • Burgess, John. 1978. Metal Ions in Solution. Chichester: Ellis Horwood. ISBN 0470262931.
  • Frey, Perry A., and Adrian D. Hegeman. 2007. Enzymatic Reaction Mechanisms. Oxford: Oxford University Press. ISBN 978-0195122589.
  • Richens, David T. 1997. The Chemistry of Aqua Ions: Synthesis, Structure, and Reactivity: A Tour Through the Periodic Table of the Elements. Chichester: Wiley. ISBN 0471970581.
  • Silverman, Richard B. 2002. The Organic Chemistry of Enzyme-Catalyzed Reactions. San Diego: Academic Press. ISBN 0126437319.
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External links

All links retrieved January 22, 2018.

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