Chemical equilibrium disruption processes in Nature, environment transformation and
importance of Le Chatelier theorem discovery for Life HOMEOSTASIS and technologies

        Āris Kaksis, 2015. year,  Riga Stradin`s University

              http://aris.gusc.lv/BioThermodynamics/74LidzsvarsDabaEngl.doc

Global observations last hundred years confirm warming of planet or increase surface temperature per
0.5° degrees of planet Earth, what accompanies environmental changes. For example, storms or storming
cyclones intensity and frequency, increases carbonic dioxide or carbonic(IV) oxide concentration in air from
0,02 % volume fractions in 1900 year to 0,038% volume fractions in 2007 year.

          Draining from reaction medium heat (cooling, what usually describe with decreasing of temperature)
has shifts the equilibrium to direction of exothermic reaction or reverse way adding heat shifts the equilibrium
to direction of endothermic reaction, et cetera in air is evolving the CO2 .

          In many discussions about chemical equilibrium nature is known example, that exist equilibrium
between carbon(IV) oxide and in water dissociated bicarbonate anion with hydrogen ions. CO2 gas dissolution
reaction is exothermic therefore warming the planet shifts equilibrium towards CO2 gas evolving direction,
because heat adding shifts equilibrium to endothermic reaction. As well planet and oceans warming increase
CO2 air concentration.
CO2vaporEngl.jpg

          Reconstruction climate of Earth shows temperature and CO2 oscillation, which 600 million years back in historical 10000
years period is observing earth warming from -50° to 45° degrees and carbon(IV) oxide gas concentration in air reaches 60%,
what corresponds 600000 ppm.
As is seen climate changes are occurring with corresponding chemical equilibrium disarranging and new equilibrium establishing,
what we can observe as CO2 concentration changes in air.

CO2conc

          

          Before 600 million years CO2 concentration in atmosphere approximately like present-day 0.03% volume fractions, what agree 300 ppm.

          Atmospheric oxygen O2 concentration approximately 1% from today’s 20.95% volume fraction was unconformable for bulk of present-day animal species.

          Approximately 600 million years back Earth was ice covered reminding Snowball Earth. Glacier fast melting provokes CO2 concentration growth up to 60% - 600000 ppm.

          Due to greenhouse effect temperature increases from -50° up to 45° degrees, what because of photosynthetic reaction brought oxygen O2 concentration fast increase above present-day 20.95% up to 30% volume fractions, and established oxygen O2 content level in atmosphere 20.95% volume fraction for next 500 million years.

         During the last 2.6 million years or so in the

Quaternary period, ice ages, also called glacial ages, were times of extreme cooling of the Earth's climate where ice sheets and other types of glacier expanded to cover large areas of land. Between ice ages there were warmer interglacial periods and we are now living during such a time.

  There have been  many ice ages during the last 2.6 million years but when people talk about the

Ice Age, they are often referring to the most recent glacial period, which start 13557 years ago and ended about
11,500 years ago and preceding warmer interglacial period end at 13557 years because as written in Indians,
Egyptians, Assyrians and Mayan calendar, the preceding proto civilization was go waste on data 11542 year B.C.
and refers to days civilization before 13557 years. What causes ice ages is not completely understood.
The composition of the atmosphere, changes in the position of our planet around the Sun, changes in ocean
currents and the Sun radiation as spot activity irregular as well as regular (11 year periods) changes are some
of the important factors that control the climate. Exist else unknown factors influence on climate? Sun and Earth
increase! Earth radius in 3000 years increases per 60 km, Mayan astronomers and to days since measure.

ice

Image: A reconstruction of the Anglian ice sheet in Precambrian North London (credit: The Natural
History Museum, London) CO2 60% and warming increased temperature shifts photo-synthesis
towards → C6H12O6 + 6 O2. Oxygena O2 concentrationa in atmosphere reaches 35% volume fraction
amount that relevente over 20,95%.

PreCembrian Ediacaran period 635 – 545 million years ago

preCambrian

Known also as the Vendian, the Ediacaran was the final stage of Pre-Cambrian time. All life in the Ediacaran
was soft-bodied - there were no bones, shells, teeth or other hard parts. As soft bodies don't fossilise very
well, remains from this period are rare. The world's first ever burrowing animals evolved in the Ediacaran,
though we don't know what they looked like. The only fossils that have been found are of the burrows
themselves, not the creatures that made them. This period gets its name from the Ediacara Hills in Australia,
where famous fossils of this age were found.

        Cambrian period 545 – 495  million years ago

Cambrian

The Cambrian is famed for its explosion of abundant and diverse life forms. Life had diversified into many
forms and many ways of living: animals now swam, crawled, burrowed, hunted, defended themselves and
hid away. Some creatures had evolved hard parts such as shells, which readily fossilised and left a clear
record behind. However, sometimes geologists get lucky and find beautiful fossils of soft and squishy
creatures - as at the Burgess Shale site. In Cambrian times there was no life on land and little or none in
freshwater - the sea was still very much the centre of living activity.

       Carbon dioxide concentration increase on air change global equilibrium for green plants
photosynthetic reaction: (red and blue light photon energy absorption)                         glucose

PhotoSynthEngl.jpg

           In global equilibrium of life nature organisms are imagine expressed as glucose (C6H12O6) and
oxygen (O2) „combusted” transforming reverse way to water and carbon dioxide. So cells and our organisms
use in photosynthetic reaction accumulated energy of red and blue light photons. In life nature occurring is
reverse reaction of photosynthesis „combustion”, of which evolved energy is used for our organism warming
and maintenance the life processes in body.
Investigations shows that 600 millions year ago in 10000 year period was observing increased oxygen concentration
on air 30% volume fractions comparing with present-day 20,95% volume fractions. Higher temperature and
greater oxygen concentration accelerate evolution of animals on Earth and scientists think, that it promote
multi cellular organisms and humans birth on planet Earth.
           Scientists in investigations have clear up, that ordinary plant species existence is possible if carbon
dioxide CO2 concentration in air do not drops below 0,005% volume fraction 50 ppm, other way green plants on
Earth perish due to insufficient material CO2 resources, which dramatically would lead to oxygen O2
extinction on planet Earth atmosphere and for us not to be what to breath and after all also what to eat,
because no more glucose C6H12O6 created, however on Earth such risk of evolution never have been exist.
           4 oxygen O2 with 4H+ from water medium adsorb deoxy T hemoglobin HbT of inspired fresh air.
4O2+4H++(His63,58)4HbTbetaVal1(NH4+PO42-G-)2<=>(H+His63,58)4Arg+His+betaVal1(NH4+)2HbR(O2)4+BPG5-
           H2COPO32--HCOPO32--COO->BPG5- is glycerate dihydroxy acid salt G- of two phosphate
2,3-esters with homeostasis concentration [BPG5-]= 5 mM and is glycolysis metabolite in erythrocytes
which regulate [O2] concentration sensitive equilibrium shift to turn transition oxy R=>deoxy T
at lowered concentration below [O2]=6•10-5M in blood plasma because of BPG5- squeeze in to cavity
due to oxygen pressure decrease as desorbs four oxygens 4 O2, and four 4 H+ following equilibrium shifts
to right oxy R=>deoxy T .
(H+His63,58)4Arg+His+betaVal1(NH4+)2HbR(O2)4+BPG5- <=>4O2+4H++(His63,58)4HbTbetaVal1(NH4+PO42-)2G-
Arterial blood homeostasis oxygen concentration is [O2]=6•10-5M which [O2] reaching tissue cells decreases below
[O2]<6•10-5 M , therefore BPG5- squeeze in to cavity Oxygen 4 O2 desorbing from oxy HbR(O2)4 supply into
solution 4H+. Lung↔tissue Homeostasis  venous deoxy HbT desorbed Oxygen O2 from hemoglobin acidify water
medium with 4H+, promoting breathe out CO2up. Respiration one CO2 molecule evolving supports in water medium
one proton H+, which desorbed form oxy HbR(O2)4 distal His63,58 histidines. Each H+ ion in respiration out CO2
shifts equilibrium to right side: 4H+ +4HCO3-+ 4Q<=>4H2O +4CO2up and pH remains constant in blood pH = 7,36 ,
as one bicarbonate ion and one hydrogen ion produce one CO2 right side.


cytosol    =>       =>               epithelial cell surface
H2CO3+ Q=H2O +CO2up

4H+ concentration increase in lungs? That shifts bicarbonate HCO3- transport through membrane with CO2breezing out. As it shows blood buffer system physiological mechanism study for transport of protons H+ and bicarbonate HCO3-ions crossing membrane channels on alveolar epithelia cell surface.

How does work Le Chatelier’s principles in equilibrium of oxygen O2 inspiration and breathe out CO2in Homeostasis

H++HCO3-+ Q endothermic<=>H2O +CO2up initial amount, concentration increase elevate CO2upoutput.
1) heating + Q shifts equilibrium right side => ;
2) hydrogenH+ion concentration (acidity) increase shifts equilibrium right side => Hb adsorbed O2 yield H+;
3) bicarbonate HCO3-concentration increase shifts equilibrium right side =>. 

Haber

           Ammoniac can obtain in hydrogen reaction with nitrogen using catalyst  porous iron Fe. At absence of catalyst reaction practically does not happen and has not established equilibrium. Therefore if hydrogen run out in air ammoniac not forms and only stand for dangerous explosion, because hydrogen reacts with oxygen if it ignite. In oil, gas and coal refining industry arises huge amount of hydrogen H2, as well hydrogen atoms containing organic compounds was heated. Up to1920 year in refinement factories hydrogen was combusted and hydrogen flame torches was factory landscape integral part, because accumulation of hydrogen mixture with oxygen is dangerous explosive.
Haber invents device for ammoniac obtaining and in 1920 year on USA and UK oil refinement factories was mounted first equipments. Le Chatlier theorem has allowed up to optimal circumstances to develop ammoniac obtaining technology. Equilibrium influences temperature, pressure. Product pressure of ammoniac diminishes, condensation into liquid due to cooling or dissolution into water. In Haber process circulate two gases nitrogen N2 and hydrogen 3H          Initially equipment durability allowed 100 MPa pressure and 200° C temperature, but at modern equipment optimal established 450° C temperature and 30 MPa pressure. As catalyst uses porous iron Fe. Obtained equilibrium mixture contains 98% ammoniac. Condensed NH3 in next box is made in water, in which dissolves NH3, or condensed and liquid product feels in transport tank. Ammoniac gas pressure decreasing pNH3↓ shifts equilibrium to right. Unused gases N2 + 3H2 returns in porous iron Fe reaction box and Haber cycle equilibrium established again during one second with 98% ammoniac volume fraction. To remove oxygen from air (N2,O2), mixture introduces in Bosh process together with methane and water (CH4, H2O) and obtains pure nit`rogen and hydrogen mixture. Heated 450° C nitrogen and hydrogen  mixture (N2 + 3H2) compressed introduces in Haber cycle reactor , but Haber process rest of mixture (N2 + 3H2) returns in reactor repeating reaction in technological cycle:

N2-3H2Eng.jpg; NH3-H2OEng.jpg

1. Gas product NH3↑ concentration is diminished dissolving in water or condensing liquid, equilibrium shifts to product NH3 right and NH3 outcome increases;
2. Increasing pressure above 30 MPa equilibrium shifts to left and product NH3 outcome decreases;
3. Decreasing pressure below 30 MPa decreases velocity of reaction on catalyst porous iron Fe surface and product
NH3 gain decreases;
4. Increasing temperature above 450° C degrees, equilibrium shifts to direction of endothermic reaction to left, towards initial compounds N2 + 3H2 and product NH3 yield decreases;
5. Decreasing temperature below 450° C degrees, equilibrium shifts to direction of exothermic reaction to right, towards product NH3 and yield increases, but decreases reaction velocity on catalyst porous iron Fe surface and product NH3 yield decreases
On year 1990 in USA have produced 50 million tons ammoniac. Ammoniac is nitrogen source for fertilizers in agricultural industry, because ammoniac is resource for nitric acid HNO3 manufacturing, but from nitric acid obtains nitric salts, which in agriculture industry designate with name salpeter. On first half 20th century Chile exports salpeter of Chile NaNO3 and from India purchased salpeter of India KNO3. Those resources exhaust in former century, which replaces Haber cyclic process technology introducing on oil and gas refinement factories.
Ammoniac solution in water call about ammoniac water. Ammoniac very good dissolves in water. In medicine shops can to purchase liquid ammonia (smelling salts), what is ammoniac solution in water :

 

              Life species on surface of Earth ozone layer cover from ultraviolet radiation of Sun. Ozone molecules O3 forms on high layers of atmosphere 10 to 35 kilometers high. Ultraviolet radiation brakes double bond of oxygen molecule O=O, because collision energy is sufficient for overcome energy barrier in reaction, that crack covalent bonds: O-O.jpg+ Q energy (ultraviolet radiation) ArowReact.jpg  O + O
           Possibility, that split oxygen atoms met each other is negligible small, therefore reverse reaction velocity is very slow due to low oxygen atoms O concentration and possible is collision with other molecule of oxygen So forms ozone: O2 + OArowReact.jpgO3. Overall reaction of equilibrium is performing as formation of two ozone molecules
O-O.jpg+ Q energy (ultraviolet radiation) +2 O2 ArowReact.jpg  O3 + O3 .
           Equilibrium shifts towards ozone formation, if increases oxygen concentration and ultraviolet radiation supplied amount of energy Q.
           Any compound, which react with ozone, dismantles ozone natural formation equilibrium in higher atmosphere layers and ozone concentration decreases, because ozone is depleted.
           Ozone forms in devices, which are mounted with ultraviolet lamps (copyist, sanitary junctions of clinics, biological laboratories, agro cultural technologies and sterilization rooms). Ozone forms in electric discharges of sparkles. For example, oxygen ozonator of Riga water refinement and in time of thunder storm. If on air in electric discharge from nitrogen and oxygen forms nitric(II) oxide:
O2 + N2 ArowReact.jpg 2 NO , which react with oxygen:
O2 + NO ArowReact.jpg 2 NO2 + O and atomic oxygen forms ozone:O2 + O ArowReact.jpg O3 .
Nitric(II) oxide also react with ozone : O3 + NO ArowReact.jpg NO2 + O2 and ozone reacting out to converts about oxygen and nitric(IV) oxide.
Thunder storm rain is fertile, because it makes richer soil with nitric oxides (NO2, NO) performing nitrates, which are valuable resource in plants life. If soil is richer with nitrates, then healthy and darker green looks plants.
Chemical equilibrium disruption processes in Nature, environment transformation and
importance of Le Chatlier theorem discovery for sciences and technologies

1. Warming of planet Earth increases carbonic dioxide gas CO2 concentration in air.

2. Carbonic dioxide gas concentration growth shifts equilibrium for green plant photosynthetic reaction to product formation and increases in reaction produced glucose C6H12O6 and oxygenO2 amount.

3. Catalysts do not change reaction equilibrium state: concentration, pressure and temperature influence on equilibrium, but increases velocity for establishing of equilibrium.

4. Haber for ammoniac synthesis cycle found optimal circumstances, applying Le Chatlier theorem and determined catalyst , which increases velocity for establishing of equilibrium.

5. Ozone equilibrium on upper atmospheric layers depends on compounds, which react out with ozone and so decreasing ozone concentration 10 to 15 kilometer high.