Orthophosphoric acid or Phosphoric(V) acid

Orthophosphoric acid or Phosphoric(V) acid is a colorless, odorless, ployprotic inorganic acid. Its
structural formula is H3PO4 and the structure of orthophosphoric acid is :-

It is a non-toxic acid, which, when pure, is a solid at room temperature and pressure and a colorless
viscous liquid at temperatures above 42 C. The conjugate base of phosphoric acid is the dihydrogen
phosphate ion, H2PO4, which in turn has a conjugate base of hydrogen phosphate, HPO24, which has
a conjugate base of phosphate, PO34 . Also Orthophosphoric acid molecules can combine with
themselves to form a variety of compounds referred to as Phosphoric acids in a more general way , eg
Metaphosphoric acid , Pyrophosphoric acid and Polyphosphoric acid. Thats the reason why
prefix ortho- is used, to distinguish the acid from related phosphoric acids.

Although phosphoric acid does not meet the strict definition of a strong acid(as indicated by its first
dissociation constant i.e Ka1 = 7.5103), its concentrated solution is acidic enough to be corrosive
thats why it is not stored in incompatible metals such as aluminium, the alloys of aluminium,
and carbon steel.

Orthophosphoric acid is a triprotic acid which is stronger than acetic acid, but weaker than sulfuric acid
and hydrochloric acid. Upon dissolving in water,it ionizes to give H2PO4,HPO42 ,PO43. The equations
are as follows-

H3PO4(s) + H2O(l) H3O+(aq) + H2PO4(aq) Ka1 = 7.5103 pKa1 = 2.12

H2PO4(aq) + H2O(l) H3O+(aq) + HPO42(aq) Ka2 = 6.2108 pKa2 = 7.21

HPO42(aq) + H2O(l) H3O+(aq) + PO43(aq) Ka3 = 2.21013 pKa3 = 12.67

Even though all three hydrogen (H) atoms are equivalent on an orthophosphoric acid molecule, the
successive Ka values differ, since it is energetically less favorable to lose another H+ if one (or more)
has already been lost and the molecule/ion is more negatively charged.

In a solution ,the relative proportions of each species is governed by the pH of solution. For large acid
concentrations, the solution is mainly dominated by the undissociated H3PO4. At 10-2 M, the pH is close
to pKa = 2.14, giving an equimolar mixture of H3PO4 and H2PO4-. Below 10-3 M, the solution is mainly
composed of H2PO4-, while HPO4-2 becoming non negligible for very dilute solutions. The
orthophosphate ion, PO4-3, is always negligible.

Remember this analysis does not take into account ion activity coefficients, so the pH and molarity of a real
phosphoric acid solution may deviate substantially from the above values
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The most common source of phosphoric acid is an 85% aqueous solution; such solutions are
colourless, odourless, and non-volatile. The 85% solution is a syrupy liquid, but still pourable. Because
of the high percentage of phosphoric acid in this reagent, at least some of the orthophosphoric acid is
condensed into polyphosphoric acids; but for the sake of labeling and simplicity, the 85% represents
H3PO4 as if it were all in the ortho form. Dilute aqueous solutions of phosphoric acid exist in the ortho
form.

PREPARATION
Phosphoric acid is produced industrially by two general routes the thermal process and the wet
process, which includes two sub-methods. The wet process dominates in the commercial sector. The
more expensive thermal process produces a purer product, which is used for applications in the food
industry.

THERMAL PROCESS

Very pure phosphoric acid is obtained by burning elemental phosphorus to produce phosphorus
pentoxide, which is subsequently dissolved in dilute phosphoric acid.

P4 + 5 O2 (excess) P4O10

P4O10 + 6 H2O(hot) 4 H3PO4

This route produces a very pure phosphoric acid, since most impurities present in the rock have been
removed when extracting phosphorus from the rock in a furnace. The end result is food-grade, thermal
phosphoric acid; however, for critical applications, additional processing to remove arsenic compounds
may be needed.

WET PROCESS

Wet-process phosphoric acid is prepared by adding sulfuric acid to tricalcium phosphate rock, typically
found in nature as apatite. The reaction is:

Ca5(PO4)3X + 5H2SO4 + 10H2O 3H3PO4 + 5CaSO42H2O + HX ( X = OH, F, Cl, Br)

The initial phosphoric acid solution may contain 2333% P2O5 (3246% H3PO4), but can be
concentrated by the evaporation of water to produce commercial- or merchant-grade phosphoric acid,
which contains about 5462% P2O5 (7585% H3PO4). Further evaporation of water
yields superphosphoric acid with a P2O5 concentration above 70% (corresponding to nearly 100%
H3PO4; however , pyrophosphoric and polyphosphoric acids will start to form, making the liquid highly
viscous).

Digestion of the phosphate ore using sulfuric acid yields the insoluble calcium sulfate (gypsum), which
is filtered and removed as phosphogypsum. Wet-process acid can be further purified by removing
fluorine to produce animal-grade phosphoric acid, or by solvent extraction and arsenic removal to
produce food-grade phosphoric acid.

The nitrophosphate process is similar to the wet process except that it uses nitric acid in place of
sulfuric acid.

Ca3(PO4)2 + 6 HNO3 + 12 H2O 2 H3PO4 + 3 Ca(NO3)2 + 12 H2O

The advantage to this route is that the coproduct, calcium nitrate is also a plant fertilizer but this method
is rarely employed because of low yield.

LABORATORY USE

A demonstrative process consists in the oxidation of red phosphorus by nitric acid.

/nPn + 5HNO3 H2O + H3PO4 + 5NO2

1

USES
The dominant use of phosphoric acid is for fertilizers. Phosphorus is one of the elements essential for
plant growth. Organic phosphates are the compounds which provide the energy for most of the
chemical reactions that occur in living cells. Therefore, enriching soils with phosphate fertilizers
enhances plant growth eg monoammonium and diammonium phosphates

NH3 + H3PO4 (NH4)H2PO4

2 NH3 + H3PO4 (NH4)2HPO4

Food additive

Food-grade phosphoric acid is used to acidify foods and beverages such as various colas and jams. It
provides a tangy or sour taste but also has the potential to cause dental erosion. Various salts of
phosphoric acid, such as monocalcium phosphate, are used as leavening agents (substance causing
expansion of doughs and batters by the release of gases within such mixtures, producing baked
products with porous structure.)

Rust removal

Phosphoric acid may be used to remove rust by direct application to rusted iron, steel tools, or other
surfaces. The phosphoric acid changes the reddish-brown iron(III) oxide, Fe2O3 (rust), to ferric
phosphate, FePO4. An empirical formula for this reaction is

2 H3PO4 + Fe2O3 2 FePO4 + 3 H2O

It provides moderate corrosion resistance (such protection is also provided by the superficially
similar Parkerizing and blued electrochemical conversion coating processes).
In medicine

Phosphoric acid is used in dentistry and orthodontics as an etching solution, to clean and roughen the
surfaces of teeth where dental appliances or fillings will be placed. Phosphoric acid is also an ingredient
in over-the-counter anti-nausea medications that also contain high levels
of sugar (glucose and fructose). This acid is also used in many teeth whiteners to eliminate plaque that
may be on the teeth before application.

Buffer Agent In Biology and Chemistry

Due to the triprotic dissociation of orthophosphoric acid, so that its conjugate bases (the phosphates
mentioned above) cover a wide pH range, and due to phosphoric acid/phosphate solutions being, in
general, non-toxic, mixtures of these types of phosphates are often used as buffering agents or to
make buffer solutions, where the desired pH depends on the proportions of the phosphates in the
mixtures. . For example, a buffer for high-performance liquid chromatography.

Other applications

Among many applications, phosphoric acid is used:

As a solution for anodizing.

As an external standard for phosphorus-31 nuclear magnetic resonance (NMR).
As a chemical oxidizing agent for activated carbon production, as used in the Wentworth process.
As the electrolyte in phosphoric-acid fuel cells.
With distilled water (23 drops per gallon) as an electrolyte in oxyhydrogen generators.
As a catalyst in the hydration of alkenes to produce alcohols, predominantly ethanol.
As an electrolyte in copper electropolishing for burr removal and circuit-board planarization.
As a flux by metal workers and hobbyists (such as model railroaders) as an aid to soldering.
In compound semiconductor processing, phosphoric acid is a common wet etching agent: for
example, in combination with hydrogen peroxide and water it is used to etch InGaAsselective to InP.
Heated in microfabrication to etch silicon nitride (Si3N4). It is highly selective in etching Si3N4 instead
of SiO2, silicon dioxide.
As a cleaner by construction trades to remove mineral deposits, cementitious smears, and hard-
water stains.
As a chelant in some household cleaners aimed at similar cleaning tasks.
In hydroponics pH solutions to lower the pH of nutrient solutions. While other types of acids can be
used, phosphorus is a nutrient used by plants, especially during flowering, making phosphoric acid
particularly desirable.
As a pH adjuster in cosmetics and skin-care products.
As a dispersing agent in detergents and leather treatment.
As an additive to stabilize acidic aqueous solutions within a wanted and specified pH range.
As a sanitizing agent in the dairy, food, and brewing industries.
As a main reactive agent in electrochemical weld cleaning.