Alwyn Dave M.

Ambatali KEMINO1- N01

Phosphorus and Iodine: An Overview
Phosphorus is a Group 15 element, along with nitrogen, arsenic, antimony and bismuth. It has an atomic number of
15, atomic mass of 31, and three main oxidation states: +3, -3, and +5. Iodine, on the other hand, is a halogen belonging to
Group 17 of the periodic table, along with F, Cl and Br. The element has an atomic number of 53, atomic mass of 127, and
five main oxidation states: -1, +1, +3, +5 and +7. Phosphorus- 31 is the stable isotope of phosphorus while Iodine-127 is
the stable isotope of iodine (Salimen, n.d.).

Geochemistry of Phosphorus and Iodine

Phosphorus is relatively more abundant compared to Iodine. In the Goldschmidt classification scheme, Phosphorus
can be classified as lithophile (rock loving), siderophile (iron loving) and biophile (found on living organisms) depending
on the circumstances. Lithophilic phosphorus exists due to redox conditions at the Earth’s surface (Pasek, 2008). It occurs
almost exclusively in nature as orthophosphate (PO 43-), principally in the mineral apatite Ca 5(PO4)3(F,Cl,OH), but also in
monazite (Ce,La,Nd,Th,Sm)(PO4,SiO4) and xenotime (YPO4). Salimen (n.d.) stated that traces of volatile phosphorus can
also be found in magmas, but there is a great variation of phosphorus content in different igneous rocks. average
concentrations of P in various rock types as: ultramafic 220 mg kg-1; basaltic 1100 mg kg-1; granitic 600–920 mg kg-1, with
a crustal average of 1120 mg kg-1. Research conducted by Wedepohl (1978) suggests that there is also a trend of increasing
phosphorus content with increasing metamorphic grade, and an inverse correlation between phosphorus content and grain
size. On the other hand, siderophilic bahavior of phosphorus exists partially under reducing conditions (Albarede, 2011).
Siderophilic phosphorus exists in forms of pallasites. Pallasites are “metallic rock” meteorites composed of olivine and
mettalic iron-nickel mixture in equal proportions. This unusual property of pallasites is due to phosphates coexisting with
the schreibersite, (Fe,Ni)3P. Phosphates exists in forms of whitlockite, Ca 3(PO4)2, farringtonite, (Mg,Fe)3(PO4)2, and
stanfieldite, Ca4(Mg,Fe)5(PO4)6, are the most widespread species (Brunet & Laporte, 1998).
Iodine, on the other hand, shares the similar properties of the other elements in the halogen group. In the
Goldschmidt classification scheme, iodine and the other halogens are classified as lithophilic elements. Salimen (n.d.)
classified iodine minerals as either hydrosoluble or not. Iodine exists as a water-soluble mineral in forms such as
schwartzembergite (Pb5IO3Cl3O3) and exists as water- insoluble mineral in forms such as iodembolite Ag(Cl,Br,I).
According to Wedepohl (1978), several properties of iodine such as its large ionic radius, possible occurrence in non-ionic
form in melted state, and its chacophilic character (ability to combine relatively less dense compounds with chalcogens
except oxygen), as stated by Fuge & Johnson (1984) are factors that affects its distribution among igneous rocks. In these
rocks, iodine content ranges from <0.02 mgkg-1 - 1.9 mg kg-1. Sedimentary rocks tend to have higher concentrations with
average iodine contents of: -recent sediments 5–200 mg/kg, carbonates 2.7 mg/kg, shales 2.3 mg/kg and sandstones 0.8
mg/kg. Organic-rich sediments are particularly enriched in iodine (Fuge & Johnson, 1986). Soil is also generally rich in
iodine, as compared to its parent rock. Most iodine from soil were derived from the atmosphere which also came from the
ocean. The ocean serves the role of being a natural reservoir of iodine in the iodine cycle with the iodine content of
approximately 60 µg. This accurately explains why soils in regions near coastal areas have a significant higher amount of
iodine than those soils in mountainous regions. Mountainous areas can act as a barrier to atmospheric iodine migration,
particularly due to iodine being washed-out by heavier rainfall (Salimen, n.d.). In natural freshwater, iodine is easily
oxidized as I-.

Phosphorus and Iodine in Biochemistry and Medical Science

Both Phosphorus and Iodine are significant in the area of biochemistry and medicine. As stated earlier, phosphorus
is also considered as a biophilic element since it plays a huge role in different chemical processes in many ecosystems.
Phosphorus exists as phosphates in different forms in biomolecules that is essential to life such as replication and information
in RNA and DNA, metabolism in forms of ATP, NADPH, and other coenzymes, and cellular structure as phospholipids
(Pasek, 2008). These essential roles of phosphorus in phosphates is possible due to thermodynamic instability coupled with
kinetic stability, charge and coordination state, and a constant oxidation state under typical redox conditions (Westheimer,
1987).
Iodine is also a biophilic element especially to marine life, due to its abundance in marine ecosystems. Iodine was
transported with organic matter into sediments. It is said that seaweeds in the brown algae family were the main source of
iodine in saltwater. Research conducted by Kaiho (2015) concluded also that microalgae also contained a concentrated
amount of iodine it is cellular structure.
Iodine is also known to be essential to humans, as it is needed for the production of the T3 and T4 hormones through
the thyroid gland. Boron & Boulpaep (2012) illustrated the following chemical reactions that showed the conversion of
iodine to thyroid hormones:
2I- → I2 (in prescence of peroxidase and H2O2)
I2 + C9H11NO3 (tyrosin) → C9H9I2NO3 (diiodotyrosin or DIT) + C9H10INO3 (monoiodotyrosin)
C9H9I2NO3 (DIT) + C9H9I2NO3 (DIT) → C15H11I4NO4 (thyroxine T4 hormone)
C9H9I2NO3 (DIT) + C9H10INO3 (monoiodotyrosin) → C15H12I3NO4 (thyroxine T3 hormone)
Iodine- containing hormones such as T3 and T4 hormones are essential for growth and development. These
hormones are being transported throughout the body where they regulate cellular metabolism. Iodine deficiency is one of
world’s public health concern due to it being the leading cause of intellectual and developmental disabilities. In most
countries, the best strategy to control iodine deficiency is by implementing the usage of iodized salt (Laar & Pelig-Ba,
2013). Iodized salt is an edible salt treated with small amounts of iodine salts, specifically NaI, NaIO 3, KI and KIO3. This
strategy has been successful over the past few decades since it does not spoil, and salt is consumed in more predictable
amounts than most other commodities. In the Philippines, an Act for Salt Iodization Nationwide (ASIN Law) was passed in
1995, in response to the increasing goiter rates due to iodine deficiencies among Filipinos. In a research conducted by Perlas
et al., (2017), it is concluded that iodine nutrition has improved in the Philippines several years after the implementation of
the ASIN Law.

Chemistry of Phosphorus- Iodides

There are several molecules containing both phosphorus and iodine. These phosphorus iodide compounds are
generally used in organic chemistry as reducing or deoxygenating agent. The simplest form of phosphorus iodide is
phosphorus triiodide. This compound can be obtained by adding iodine to a solution of carbon disulfide and white
phosphorus.
P4 + 6 I2 → 4 PI3
Phosphorus triiodide can be used for the conversion of primary or secondary alcohols to alkyl iodides. The hydrolysis
of PI3 also yields phosphorous acid, phosphine, phosphoric acid, hydrophosphorous acid and other products which have not
yet been isolated as pure compound (Kirsanov & Gorbadenko, 1986).

PI3 + 3 CH3OH → 3 CH3I + H3PO3

H2O + PI3 → 2HI + H3PO3
H2O + PI3 → HI + H3PO3 + PH3 (small amount)
NaHCO3 + PI3 → Na2HPO3 (large amount) + Na2HPO4 + NaH2PO2 + others
Another form of phosphorus iodide that exists is in the form of P 2I4. Diphosphorus tetraiodide is an orange
crystalline solid. The phosphorus in this compound has an oxidation state of +2. This compound is used as a reducing agent
and can easily synthesized by the disproportionation of phosphorus triiodide in dry ether (Kirsanov & Gorbadenko, 1986).
2 PI3 → P2I4 + I2
According to Krief & Telvekar (2009), diphosphorus tetraiodide is used as a deoxygenating agent. It is commonly
used in organic reactions which involves deprotecting acetals and ketals to aldehydes and ketones, and for converting
epoxides into alkenes and aldoximes into nitriles. It can also be used to cyclize 2-aminoalcohols to aziridines, as stated by
Suzuki & Tani (1985), and to convert α,β-unsaturated carboxylic acids to α,β-unsaturated bromides (Telvekar & Chettiar,
2007).
Kirsanov & Gorbadenko (1986) showed other forms of phosphorus iodide molecules that exist, but these molecules
are also bonded to chalcogens like oxygen, sulfur and selenium. In order to synthesize phosphorus oxyiodide, phosphorus
oxychloride must react with lithium iodide. POI3 is dark violet crystalline substance that resembles iodine in appearance,
and has a melting point ranging from 50oC to 53oC.
POCl3 + 3LiI → 3LiC1 + POI3
On the other hand, a chemical reaction between phosphorus triiodide and and sulfur in carbon disulfide solution
would yield a brick red substance, phosphorus thioiodide. It has a melting point ranging between 46 oC and 48oC.
8P13 + S8 → 8PSI3
In additional, in a boiling carbon disulfide solution, phosphorus triodide can also interact with selenium in order to
obtain dark brown phosphorus selenide iodide crystals. This compound has a melting point ranging from 35 oC and 37oC.

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