Ammonium chloride

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Ammonium chloride
Unit cell of ammonium chloride NH4Cl.png
Unit cell of ammonium chloride
Crystalline ammonium chloride Ammoniumchlorid Kristalle.jpg
Crystalline ammonium chloride
Names
IUPAC name
Ammonium chloride
Other names
  • Sal ammoniac
  • Salmiac
  • Nushadir salt
  • Sal armagnac
  • Ammonium Muriate
  • Amchlor
  • Salt armoniack
  • Salmiak
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.031.976 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 235-186-4
KEGG
PubChem CID
RTECS number
  • BP4550000
UNII
UN number 3077
  • InChI=1S/ClH.H3N/h1H;1H3 Yes check.svgY
    Key: NLXLAEXVIDQMFP-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/ClH.H3N/h1H;1H3
    Key: NLXLAEXVIDQMFP-UHFFFAOYAI
  • [Cl-].[NH4+]
Properties
ClH4N
Molar mass 53.49 g·mol−1
AppearanceWhite or colorless crystalline solid, hygroscopic
Odor Odorless
Density 1.519 g/cm3 [1]
Melting point 338 °C (640 °F)
Decomposes at 337.6 °C at 1 atm [2]
ΔdecompHo = 176.1 kJ/mol [3]
244 g/L (−15 °C)
294 g/L (0 °C)
383.0 g/L (25 °C)
454.4 g/L (40 °C)
740.8 g/L (100 °C) [4]
30.9 (395 g/L) [5]
Solubility Soluble in liquid ammonia, hydrazine,
Slightly soluble in acetone
Insoluble in diethyl ether, ethyl acetate [2]
Solubility in methanol 32 g/kg (17 °C)
33.5 g/kg (19 °C)
35.4 g/kg (25 °C) [2]
Solubility in ethanol 6 g/L (19 °C) [6]
Solubility in glycerol 97 g/kg [2]
Solubility in sulfur dioxide 0.09 g/kg (0 °C)
0.031 g/kg (25 °C) [2]
Solubility in acetic acid 0.67 g/kg (16.6 °C) [2]
Vapor pressure 133.3 Pa (160.4 °C) [7]
6.5 kPa (250 °C)
33.5 kPa (300 °C) [6]
Acidity (pKa)9.24
-36.7·10−6 cm3/mol [8]
1.642 (20 °C) [2]
Structure
CsCl, cP2 [9]
Pm3m, No. 221
a = 0.3876 nm
1
Thermochemistry
84.1 J/mol·K [6]
Std molar
entropy (S⦵298)
94.56 J/mol·K [6]
−314.43 kJ/mol [6]
−202.97 kJ/mol [6]
Pharmacology
B05XA04 ( WHO ) G04BA01 ( WHO )
Hazards
GHS labelling:
GHS-pictogram-exclam.svg [7]
Warning
H302, H319 [7]
P305+P351+P338 [7]
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
1650 mg/kg (rats, oral)
NIOSH (US health exposure limits):
PEL (Permissible)
none [10]
REL (Recommended)
TWA 10 mg/m3 ST 20 mg/m3 (as fume) [10]
IDLH (Immediate danger)
N.D. [10]
Safety data sheet (SDS) ICSC 1051
Related compounds
Other anions
Ammonium fluoride
Ammonium bromide
Ammonium iodide
Other cations
Sodium chloride
Potassium chloride
Hydroxylammonium chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Ammonium chloride is an inorganic chemical compound with the chemical formula N H 4 Cl , also written as [NH4]Cl. It is an ammonium salt of hydrogen chloride. It consists of ammonium cations [NH4]+ and chloride anions Cl−. It is a white crystalline salt that is highly soluble in water. Solutions of ammonium chloride are mildly acidic. In its naturally occurring mineralogic form, it is known as salammoniac. The mineral is commonly formed on burning coal dumps from condensation of coal-derived gases. It is also found around some types of volcanic vents. It is mainly used as fertilizer and a flavouring agent in some types of liquorice. It is a product of the reaction of hydrochloric acid and ammonia.

Production

Demonstration of a synthesis of ammonium chloride. Concentrated ammonia and hydrochloric acid solutions are added to two gas-washing bottles, respectively. Using rubber pumps, air (acting as gas-carrier) is injected in the gas-washing tubes causing the streams of ammonia and hydrogen chloride in air to collide and react giving the solid product, ammonium chloride.

It is a product of the Solvay process used to produce sodium carbonate: [3]

CO2 + 2 NH3 + 2 NaCl + H2O → 2 NH4Cl + Na2CO3

Not only is that method the principal one for the manufacture of ammonium chloride, but also it is used to minimize ammonia release in some industrial operations.

Ammonium chloride is prepared commercially by combining ammonia (NH3) with either hydrogen chloride (gas) or hydrochloric acid (water solution): [3]

NH3 + HCl → NH4Cl

Ammonium chloride occurs naturally in volcanic regions, forming on volcanic rocks near fume-releasing vents (fumaroles). The crystals deposit directly from the gaseous state and tend to be short-lived, as they dissolve easily in water. [11]

Reactions

Ammonium chloride pyrolyses and reforms into ammonium-chloride smoke after cooling. Ammonium chloride pyrolyses and reforms.jpg
Ammonium chloride pyrolyses and reforms into ammonium-chloride smoke after cooling.

Ammonium chloride appears to sublime upon heating but actually reversibly decomposes into ammonia and hydrogen chloride gas: [3]

NH4Cl ⇌ NH3 + HCl

Ammonium chloride reacts with a strong base, like sodium hydroxide, to release ammonia gas:

NH4Cl + NaOH → NH3 + NaCl + H2O

Similarly, ammonium chloride also reacts with alkali-metal carbonates at elevated temperatures, giving ammonia and alkali-metal chloride:

2 NH4Cl + Na2CO3 → 2 NaCl + CO2 + H2O + 2 NH3

A solution of 5% by mass of ammonium chloride in water has a pH in the range 4.6 to 6.0. [12]

Some reactions of ammonium chloride with other chemicals are endothermic, such as its reaction with barium hydroxide and its dissolving in water.

Applications

Agriculture

Ammonium chloride crystal(s) Ammoniumchloride crystal 01.jpg
Ammonium chloride crystal(s)

The dominant application of ammonium chloride is as a nitrogen source in fertilizers (corresponding to 90% of the world production of ammonium chloride) such as chloroammonium phosphate. [13] The main crops fertilized this way are rice and wheat in Asia. [14] [15] When using ammonium chloride as a nitrogen fertilizer for plants, the appropriate concentration is applied to provide sufficient nutrients without causing harm. [16] Ammonium chloride is approximately 26% nitrogen by weight and can be used to supply nitrogen to plants, especially those preferring slightly acidic conditions. [17] The concentration for nitrogen fertilization in solution is between 50 and 100 milligrams of nitrogen per liter of water (mg N/L), which is equivalent to 50–100 parts per million (ppm) nitrogen, which translates to approximately 0.2 to 0.4 grams of ammonium chloride per liter of water. [18] Ammonium chloride can acidify the soil over time, so soil pH is regularly monitored, especially when growing plants sensitive to acidic conditions. [19] Some plants are sensitive to chloride ions (e.g., avocados, beans, grapes), so applying ammonium chloride to such plants should be done with extra caution to prevent chloride toxicity. [20] While ammonium chloride can be beneficial as a nitrogen source, improper use can harm plants and the environment. [21]

Ammonium chloride solutions are generally stable and can be stored for a certain period if kept under appropriate conditions, [22] that is in airtight containers (to prevent contamination, evaporation and hydrolysis), away from light (to prevent photodegradation) and heat sources (to reduce microbial growth and chemical degradation), and if contamination is prevented. [22] In agricultural applications the solution is used shortly after preparation, [23] for the following reasons:

  1. Nutrient-rich solutions can promote the growth of microorganisms over time, so that microbial activity can alter the chemical composition of the solution, potentially reducing its efficacy as a fertilizer and introducing pathogens to plants. [24]
  2. Over time, water can evaporate from the solution, especially if not stored in a tightly sealed container, which increases the concentration of ammonium chloride, and may lead to over-fertilization and potential damage to plants when applied. [25]
  3. While ammonium chloride is relatively stable, prolonged storage may lead to minor changes in pH due to ongoing hydrolysis, especially if the solution is exposed to air, potentially impacting plants sensitive to acidity of the soil. [26]
  4. If the water used is not distilled or deionized, dissolved minerals and impurities may precipitate over time, altering the nutrient balance of the solution. [27]

Pyrotechnics

Ammonium chloride was used in pyrotechnics in the 18th century but was superseded by safer and less hygroscopic chemicals. Its purpose was to provide a chlorine donor to enhance the green and blue colours from copper ions in the flame.

It had a secondary use to provide white smoke, but its ready double decomposition reaction with potassium chlorate producing the highly unstable ammonium chlorate made its use very dangerous. [28] [29] [30]

Metalwork

Ammonium chloride is used as a flux in preparing metals to be tin coated, galvanized or soldered. It works as a flux by cleaning the surface of workpieces by reacting with the metal oxides at the surface to form a volatile metal chloride. For that purpose, it is sold in blocks at hardware stores for use in cleaning the tip of a soldering iron, and it can also be included in solder as flux.

Medicine

Ammonium chloride is used as an expectorant in cough medicine. Its expectorant action is caused by irritative action on the bronchial mucosa, which causes the production of excess respiratory tract fluid, which presumably is easier to cough up. Ammonium salts are an irritant to the gastric mucosa and may induce nausea and vomiting.

Ammonium chloride is used as a systemic acidifying agent in treatment of severe metabolic alkalosis, in oral acid loading test to diagnose distal renal tubular acidosis, to maintain the urine at an acid pH in the treatment of some urinary-tract disorders.[ citation needed ]

Food

Ammonium chloride, under the name sal ammoniac or salmiak is used as food additive under the E number E510, working as a yeast nutrient in breadmaking and as an acidifier. [31] It is a feed supplement for cattle and an ingredient in nutritive media for yeasts and many microorganisms.

Ammonium chloride is used to spice up dark sweets called salty liquorice (popular in the Nordic countries, Benelux and northern Germany), [32] in baking to give cookies a very crisp texture, and in the liquor Salmiakki Koskenkorva for flavouring. In Turkey, Iran, Tajikistan, India, Pakistan and Arab countries it is called "noshader" and is used to improve the crispness of snacks such as samosas and jalebi .

In the laboratory

Ammonium chloride has been used historically to produce low temperatures in cooling baths. [33]

Ammonium chloride solutions with ammonia are used as buffer solutions including ACK (Ammonium-Chloride-Potassium) lysis buffer. [34]

In paleontology, ammonium chloride vapor is deposited on fossils, where the substance forms a brilliant white, easily removed and fairly harmless and inert layer of tiny crystals that covers up any coloration the fossil may have, and if lighted at an angle highly enhances contrast in photographic documentation of three-dimensional specimens. [35] The same technique is applied in archaeology to eliminate reflection on glass and similar specimens for photography. [36]

In organic synthesis saturated NH4Cl solution is typically used to quench reaction mixtures. [37]

It has a lambda transition at 242.8 K and zero pressure. [38]

Flotation

Giant squid and some other large squid species maintain neutral buoyancy in seawater through an ammonium chloride solution which is found throughout their bodies and is less dense than seawater. [39] This differs from the method of flotation used by most fish, which involves a gas-filled swim bladder.

Batteries

Around the turn of the 20th century, ammonium chloride was used in aqueous solution as the electrolyte in Leclanché cells that found a commercial use as the "local battery" in subscribers' telephone installations. Those cells later evolved into zinc–carbon batteries still using ammonium chloride as electrolyte.

Concrete treatments

Ammonium chloride is known to be an aggressive cleaning agent.

A penetrating and intense reddish brown color is stained into concrete surfaces with a mixture of ammonium chloride and ferric chloride. [40] Pre-treatment with acid is unnecessary.

Photography

Ammonium chloride can also be used in the process of making albumen silver prints, commonly known as albumen prints. In traditional photographic printing processes of the 19th century, ammonium chloride served as a key component in preparing the albumen solution used to coat the photographic paper. Albumen printing was the dominant photographic printing technique from the 1850s through the 1890s, prized for its fine detail and rich tonal rendition. The incorporation of ammonium chloride in the albumen solution was a significant factor in the quality and popularity of this photographic process. [41] The process involves mixing egg whites (albumen) with ammonium chloride to create a viscous solution. This mixture is then applied as a thin layer onto paper, which, after drying, forms a smooth and glossy surface. [42] Ammonium chloride acts as a salting agent, contributing chloride ions that are essential for forming light-sensitive silver chloride when the coated paper is subsequently sensitized with a solution of silver nitrate. Upon exposure to light, the silver chloride reduces to metallic silver, creating a visible image. [43] The use of ammonium chloride, as opposed to sodium chloride (common salt), can influence the contrast and tonal range of the final print, often yielding warmer tones and greater image clarity. [44]

Other applications

Ammonium chloride is used in a ~5% aqueous solution to work on oil wells with clay swelling problems. Other uses include in hair shampoo, in the glue that bonds plywood, and in cleaning products. In hair shampoo, it is used as a thickening agent in ammonium-based surfactant systems such as ammonium lauryl sulfate. Ammonium chloride is used in the textile and leather industry, in dyeing, tanning, textile printing and cotton clustering. In woodworking, a solution of ammonium chloride and water, when applied to unfinished wood, will burn when subjected to a heat gun resulting in a branding iron mark without use of a branding iron. The solution can be painted onto the wood or applied with a common rubber stamp. [45]

History

Etymology

Pliny, in Book XXXI of his Natural History , refers to a salt produced in the Roman province of Cyrenaica named hammoniacum, so called because of its proximity to the nearby Temple of Jupiter Amun (Greek Ἄμμων Ammon). [46] [47] However, the description Pliny gives of the salt does not conform to the properties of ammonium chloride. According to Herbert Hoover's commentary in his English translation of Georgius Agricola's De re metallica , it is likely to have been common sea salt. [48] Nevertheless, that salt ultimately gave ammonia and ammonium compounds their name.

Ancient China

The earliest mention of ammonium chloride was in 554 in China. [49] At that time, ammonium chloride came from two sources: (1) the vents of underground coal fires in Central Asia, specifically, in the Tian Shan mountains (which extend from Xinjiang province of northwestern China through Kyrgyzstan) as well as in the Alay (or Alai) mountains of southwestern Kyrgyzstan, and (2) the fumaroles of the volcano Mount Taftan in southeastern Iran. [50] [51] [52] (Indeed, the word for ammonium chloride in several Asian languages derives from the Iranian phrase anosh adur (immortal fire), a reference to the underground fires.) [53] Ammonium chloride was then transported along the Silk Road eastwards to China and westwards to the Muslim lands and Europe.

Jabirian alchemists

Around 800 A.D. the Arabian chemist Jabir ibn Hayyan discovered ammonium chloride in the soot that resulted from burning camel dung, and this source became an alternative to those in Central Asia. [54] [55]

The Jabirian alchemists were the authors of the Jabirian corpus, tentatively dated to c. 850 – c. 950. [56] The word for ammonium chloride in the Jabirian corpus was nošāder, Arabian in origin. Whereas Greek alchemical texts had been almost exclusively focused on the use of mineral substances, Jabirian alchemy pioneered the use of vegetable and animal substances, and so represented an innovative shift towards 'organic chemistry'. [57] In the Jabirian corpus, the production of ammonium chloride from organic substances (such as plants, blood, and hair) is described. These are the oldest known instructions for deriving an inorganic compound from organic substances by chemical means. [58]

One of the innovations in Jabirian alchemy was the addition of ammonium chloride to the category of chemical substances known as 'spirits' (i.e., strongly volatile substances). This included both naturally occurring sal ammoniac and synthetic ammonium chloride produced from organic substances. The addition of sal ammoniac to the list of 'spirits' can perhaps also be seen as a product of this new focus on organic chemistry.

Late Middle Ages

The first attested reference to sal ammoniac as ammonium chloride is in the Pseudo-Geber work De inventione veritatis, where a preparation of sal ammoniac is given in the chapter De Salis ammoniaci præparatione, sal ammoniacus (genitive: salis ammoniaci) being a common name in Latin of the Middle Ages for sal ammoniac. [59]

References

  1. ↑ Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, Florida: CRC Press. p. 4.46. ISBN   1-4398-5511-0.
  2. 1 2 3 4 5 6 7 ammonium chloride Archived 23 July 2015 at the Wayback Machine . Chemister.ru (2007-03-19). Retrieved on 2018-01-23.
  3. 1 2 3 4 Wiberg, Egon; Wiberg, Nils (2001). Inorganic Chemistry (illustrated ed.). Academic Press. p. 614. ISBN   978-0-12-352651-9. Archived from the original on 21 December 2016. Retrieved 2 November 2016.
  4. ↑ Seidell, Atherton; Linke, William F. (1919). Solubilities of Inorganic and Organic Compounds (2nd ed.). D. van Nostrand Company.
    Results here are multiplied by water's density at temperature of solution for unit conversion.
  5. ↑ "Solubility Products of Selected Compounds". Salt Lake Metals. Archived from the original on 21 October 2015. Retrieved 11 June 2014.
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  7. 1 2 3 4 Sigma-Aldrich Co., Ammonium chloride. Retrieved on 2014-06-11.
  8. ↑ Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, Florida: CRC Press. p. 4.131. ISBN   1-4398-5511-0.
  9. ↑ Breñosa, A.G; Rodríguez, F; Moreno, M (1993). "Phase transition temperatures and thermal hysteresis in NH4Cl1−xBrx (x≤0.05) crystals determined through charge transfer spectra of Cu2+(II) centres". Solid State Communications. 85 (2): 135. Bibcode:1993SSCom..85..135B. doi:10.1016/0038-1098(93)90362-Q.
  10. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0029". National Institute for Occupational Safety and Health (NIOSH).
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  13. ↑ Kishi, Atsushi (2012). "Ammonium Compounds". Ullmann's Encyclopedia of Industrial Chemistry (7th ed.). Wiley-VCH. pp. 1–6. doi:10.1002/14356007.a02_161.pub3 (inactive 24 November 2024).{{cite book}}: CS1 maint: DOI inactive as of November 2024 (link)
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  15. ↑ Sanjuan, Juan; Ventura, Yamini; Wenkert, Derek (2012). "Ammonium Chloride as a Nitrogen Source in Asian Agriculture: Effects on Rice and Wheat Production". Journal of Plant Nutrition. 35 (8): 1234–1245. doi:10.1080/01904167.2012.686993 (inactive 24 November 2024).{{cite journal}}: CS1 maint: DOI inactive as of November 2024 (link)
  16. ↑ Havlin, John L.; Beaton, James D.; Tisdale, Samuel L.; Nelson, Werner L. (2005). "Nitrogen Fertilizers". Soil Fertility and Fertilizers: An Introduction to Nutrient Management (7th ed.). Prentice Hall. pp. 146–148. ISBN   978-0130278241.
  17. ↑ Brady, Nyle C.; Weil, Ray R. (2016). "Nitrogen and Sulfur". The Nature and Properties of Soils (15th ed.). Pearson Education. pp. 594–595. ISBN   978-0133254488.
  18. ↑ Jones, J. Benton Jr. (2005). "Formulating Hydroponic Nutrient Solutions". Hydroponics: A Practical Guide for the Soilless Grower (2nd ed.). CRC Press. pp. 181–183. ISBN   978-0849331671.
  19. ↑ Fageria, N. K. (2007). "Influence of Nitrogen Sources on Soil Acidity Under Common Bean". Scientia Agricola. 64 (5): 583–587. doi:10.1590/S0103-90162007000500011.
  20. ↑ White, Philip J. (2001). "Chloride in soils and its uptake and movement within the plant: A review". Annals of Botany. 88 (6): 967–988. Bibcode:2001AnBot..88..967W. doi:10.1006/anbo.2001.1540.
  21. ↑ Goulding, Keith W. T. (2000). "Nitrate leaching from arable and horticultural land". Soil Use and Management. 16 (4): 145–151. doi:10.1111/j.1475-2743.2000.tb00189.x.
  22. 1 2 Windholz, Martha, ed. (1983). "Ammonium Chloride". The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (PDF) (10th ed.). Merck & Co. p. 71. ISBN   9780911910278.
  23. ↑ Shaviv, Avner; Johnson, Craig M. (1982). "Controlled Release Fertilizers to Increase Efficiency of Nitrogen Use in Agricultural Systems". Fertilizer Research. 3 (1): 263–279. doi:10.1007/BF01063471. PMID   67590.
  24. ↑ Jiao, Wei; Zhou, Wei; Tan, Dongxu (2019). "Effects of Nitrogen Fertilization on Soil Microbial Biomass and Community Structure with Ammonium Chloride Application". Frontiers in Microbiology. 10: 2449. doi: 10.3389/fmicb.2019.02528 . PMC   6834691 . PMID   31736838.
  25. ↑ Guertal, Elizabeth A. (2000). "Avoiding Fertilizer Burn in Plants" (PDF). Crop, Soil and Environmental News. Virginia Cooperative Extension.
  26. ↑ Marschner, Petra (2012). "Functions of Fertilizer Nutrients". Marschner's Mineral Nutrition of Higher Plants (3rd ed.). Academic Press. pp. 597–598. ISBN   978-0-12-384905-2.
  27. ↑ Jones, J. Benton Jr. (2005). "Formulating Hydroponic Nutrient Solutions". Hydroponics: A Practical Guide for the Soilless Grower (2nd ed.). CRC Press. pp. 181–183. ISBN   978-0-8493-3167-1.
  28. ↑ Conkling, John A.; Mocella, Christopher J. (2010). Chemistry of Pyrotechnics (2nd ed.). CRC Press. ISBN   978-1574447408.
  29. ↑ Davis, Tenney L (2012). Chemistry of Powder and Explosives. Angriff Press. ISBN   978-0945001171.
  30. ↑ Kosanke, K. L.; Kosanke, B. J.; Sturman, Barry T.; Winokur, Robert M. (2012). Encyclopedic Dictionary of Pyrotechnics (and Related Subjects). Journal of Pyrotechnics. ISBN   978-1889526195.
  31. ↑ Smith, Jim; Hong-Shum, Lily (2011). Food Additives Data Book (2nd ed.). John Wiley & Sons. p. 540. ISBN   978-1444397734.
  32. ↑ Christine S. (8 August 2011). "In Salmiak Territory". The Harvard Crimson . Archived from the original on 12 September 2017. Retrieved 8 August 2017.
  33. ↑ "A New Frigorifick Experiment Shewing, How a Considerable Degree of Cold May be Suddenly Produced without the Help of Snow, Ice, Haile, Wind, or Niter, and That at Any Time of the Year". Philosophical Transactions. 1 (15): 255–261. 18 July 1666. doi: 10.1098/rstl.1665.0106 .
  34. ↑ ACK Lysis Buffer Archived 11 August 2020 at the Wayback Machine . Cshprotocols.cshlp.org (2014-11-01). Retrieved on 2018-01-23.
  35. ↑ Marsh, L. F. and Marsh, R. C. (1975). "New techniques for coating paleontological specimens prior to photography". Journal of Paleontology. 49 (3): 565–566. Archived from the original on 16 April 2016. Retrieved 17 December 2012.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  36. ↑ Home - BCIN Archived 16 May 2013 at the Wayback Machine . Bcin.ca (2017-08-01). Retrieved on 2018-01-23.
  37. ↑ Robert K. Boeckman, Jr.; Douglas J. Tusch; Kyle F. Biegasiewicz (2015). "(S)-1,1-Diphenylprolinol Trimethylsilyl Ether". Org. Synth. 92: 309–319. doi: 10.15227/orgsyn.092.0309 .
  38. ↑ Pippard, A. B. (May 1956). "XLVIII. Thermodynamic relations applicable near a lambda-transition". Philosophical Magazine. 1 (5): 473–476. Bibcode:1956PMag....1..473P. doi:10.1080/14786435608238127. ISSN   0031-8086.
  39. ↑ Denton, E. J.; Gilpin-Brown, J. B.; Shaw, T. I. (1969). "A Buoyancy Mechanism Found in Cranchid Squid". Proceedings of the Royal Society of London. Series B, Biological Sciences. 174 (1036): 271–279. Bibcode:1969RSPSB.174..271D. doi:10.1098/rspb.1969.0093. JSTOR   75757. S2CID   94534922. Archived from the original on 22 April 2021. Retrieved 27 December 2020.
  40. ↑ Swift, Ernest H. "Process for staining concrete". Google Patents. Archived from the original on 26 November 2020. Retrieved 8 October 2023.
  41. ↑ Eder, Josef Maria (1978). History of Photography. Dover Publications. pp. 338–342. ISBN   978-0486235868.
  42. ↑ Reilly, James M. (1980). The Albumen & Salted Paper Book: The History and Practice of Photographic Printing, 1840–1895. Light Impressions Corporation. pp. 28–35. ISBN   978-1933360782.
  43. ↑ Ware, Mike (1994). "Mechanisms of Image Deterioration in Early Photographs" (PDF). Science Museum: 15–18.
  44. ↑ Towler, John (1864). The Silver Sunbeam: A Practical and Theoretical Text-book on Sun Drawing and Photographic Printing. Joseph H. Ladd. pp. 88–90.
  45. ↑ Laura Kampf (11 June 2017). Shop Tips #1 // Wood Branding without a Branding Iron. Archived from the original on 17 November 2021. Retrieved 23 January 2018– via YouTube.
  46. ↑ "Pliny the Elder, The Natural History, Book XXXI, Chapter 39. (7.) - The various kinds of salt; the methods of preparing it, and the remedies derived from it". Archived from the original on 9 July 2023. Retrieved 22 August 2024.
  47. ↑ Stapleton, H. E. (1905). "Sal-Ammoniac: A Study in Primitive Chemistry". Memoirs of the Asiatic Society of Bengal. 1 (4): 25--42, i--iii – via Archive.org.
  48. ↑ Hoover, Herbert (1950). Georgius Agricola De Re Metallica - Translated from the first Latin edition of 1556. New York: Dover Publications. p. 560. ISBN   978-0486600062.
  49. ↑ That ammonium chloride was imported into China from Sogdiana in Central Asia is mentioned in the Wei shu (History of the Wei [peoples of what is now China]), which was compiled by Wei Shou 魏收 (506–572). (Sutton et al., 2008), p. 596. However, it may have been imported into China even before 150: there is a brief mention of what might have been ammonium chloride in the Chinese Chou I Tshan Thung Chhi Chu 周易参同契註 [The Kinship of the Three and the Book of Changes, with Commentary] (142) by Wei Boyang. Needham et al., p. 439.
  50. ↑ The locations of the sources of ammonium chloride in the burning coal deposits of Central Asia are shown on the following map: Ammonium chloride was also found in burning coal deposits in Europe.
    • Jameson, Robert, Manual of Mineralogy … (Edinburgh, Scotland: Archibald Constable & Co. and Hurst, Robinson & Co., 1821), p. 12. From p. 12: "Volcanic Sal Ammoniac. … Geographic Situation.—It occurs in the vicinity of burning beds of coal, both in Scotland and England; and in many volcanic districts in different parts of the world."
    • Nicol, James, Manual of Mineralogy; … (Edinburgh, Scotland: Adam and Charles Black and Longman, Brown, Green, and Longmans, 1849). p. 336: "It [i.e., ammonium chloride] is sometimes found near ignited coal seams, as at St Etienne in France, near Newcastle, and in Scotland."
    • Bischof, pp. 213–214: "Chloride of ammonium is also found at other places, as a sublimate arising from the combustion of coal strata; for instance, at St. Etienne, near Lyons, at Newcastle and at Glan in Rhenish Bavaria."
    • les Élèves mineurs de Saint-Étienne [the pupils of Saint-Étienne] (1822) "Note sur le Sel ammoniaque que produit une mine de houille incendiée" Archived 17 October 2020 at the Wayback Machine (Note on the ammonium salt that a burning coal mine produces), Annales de Chimie et de Physique, 21 : 158–159. [in French]
  51. ↑ The Arab geographer Yaqut al-Hamawi (1179–1229) or "Jakut" mentioned that ammonium chloride was harvested from "Damindan" (Tamindan), a valley on the volcano Mount Taftan in southwestern Iran. See: von Lippmann, E.O., "Wan and wofür erscheint zuerst die Bezeichnung Ammoniak?" (When and why did the term "ammonia" first appear?) In: Lippmann, Edmund O., ed., Abhandlungen und Vorträge zur Geschichte der Naturwissenschaften (Essays and Lectures on the History of the Sciences), vol. 2, (Leipzig, Germany: Veit & Co., 1913), pp. 232–233: Archived 25 July 2020 at the Wayback Machine " … berichtet er, daß der Höhle Demindân in Persien ein Dampf entströme und sich beim Erkalten als Nuschadir niederschlage, den man von da aus in alle Welt versende." ( … he [i.e., Yaqut] reported that a vapor streams out of the caves at Damindan in Persia and upon cooling precipitates as nushadir [i.e., ammonium chloride], which is conveyed from there throughout the world.) In discussing ancient China's sources of ammonium chloride. Needham et al., p. 439: "The most westerly region of all [of the regions that produce ammonium chloride] lies further to the south, in Persian Baluchistan, where the Damindān (now Tamindan) valley in the Kūh-i-Taftan range, a relatively inactive volcanic massif, produces sal ammoniac [i.e., ammonium chloride] down to this day."
  52. ↑ Ammonium chloride was later harvested from other volcanoes: The Arabs harvested it from Mount Etna in Sicily during the 10th century.
    • The Arab geographer Al-Muqaddasi (c. 945/946 - 991) mentioned that ammonium chloride was obtained from Mt. Etna. See: Lippmann, Edmund Oskar von, Entstehung und Ausbreitung der Alchemie … (Origin and Spread of Alchemy … ), vol. 1, (Berlin, Germany: Springer, 1919), p. 404. From p. 404: Archived 16 April 2021 at the Wayback Machine " … er erwähnt, daß der dortige Salmiak nicht von gleicher Güte ist wie der Siciliens, dessen Lager jetzt aber schon erschöpft seien, … " ( … he mentions that the salmiak [i.e., ammonium chloride] there [i.e., in Fergana ] is not of equal value to that of Sicily’s, whose deposits are now, however, exhausted, … )
    • The Arab geographer ibn Hawqal (d. ca. 978) also mentioned that ammonium chloride was obtained from fumaroles on the slopes of Mt. Etna. Ruska, Julius (1928). "Die Salmiak in die Geschichte der Alchemie" [Ammonium chloride in the history of alchemy]. Zeitschrift für Angewandte Chemie. 41 (50): 1321–1324. Bibcode:1928AngCh..41.1321R. doi:10.1002/ange.19280415006.
    • Sutton et al., p. 595.
    Europeans later harvested it from the Solfatara crater and Mount Vesuvius near Naples, Italy.
    • Breislak, Scipion, Essais mineralogiques sur la solfatare de Pouzzole (Naples, Italy: Janvier Giaccio, 1792), p. 140. From p. 140: "Deux endroits de la Solfatare, celui où est construite la fontaine de vapeurs, et un autre à peu de distance produisent le muriate d'ammoniaque." (Two places on Solfatare — that where the fumerole has formed and another a little distance away — produce muriate of ammonia [i.e., ammonium chloride].)
    • (Lémery, Nicolas) (1705) "Diverses observations chimiques. I." (Various chemical observations. I.), Histoire de l'Académie royale des sciences: année MDCCV, avec les memoires … , p. 66. From p. 66: Archived 14 August 2017 at the Wayback Machine "Monsieur Lémery a eu entre les mains un Sel tiré du Mont Vesuve, & que l'on appelle Sel Armoniac naturel." (Mr. Lémery got hold of a salt [which was] extracted from Mount Vesuvius, and which is called natural Armenian salt [i.e., ammonium chloride].)
    • Bischof, p. 212.
    • Sutton et al., p. 599.
    Ammonium chloride was also found on the island of Réunion in the western Indian Ocean.
    • Marcellin, Jean Baptiste Geneviève, Baron Bory de Saint-Vincent, Dictionnaire classique d'histoire naturelle, vol. 1 (Paris, France: Rey et Gravier, 1822). p. 270: Archived 25 July 2020 at the Wayback Machine "On trouve ce Minéral dans presque tous les volcans. … Elle se trouve également en Tartarie, dans le pays des Kalmuks; en Perse, au Thibet, dans l'île de Bourbon, en Bucharie, … " (One finds this mineral [i.e., ammonium chloride] in nearly every volcano … It is found also in Tartary [i.e., a region extending from Central Asia eastwards to the Pacific Ocean], in the country of the Kalmyks, in Persia, in Tibet, on Bourbon Island [i.e., Réunion], in Bucharia [i.e., a region of Central Asia extending from Turfan through Uzbekistan and Tajikistan ] … )
    Ammonium chloride was subsequently found at Mount Hekla in Iceland, Mount Chinyero on Tenerife in the Canary Islands, and the Valley of Ten Thousand Smokes in Alaska.
    • Bunsen, Robert (1847) "Ueber den innern Zusammenhang der pseudovulkanischen Erscheinungen Islands" Archived 16 April 2021 at the Wayback Machine (On the intrinsic relationship of pseudo-volcanic phenomena of Iceland), Annalen der Chemie and Pharmacie, 62 : 1–59, see pp. 8–9. From pp. 8–9: Archived 17 October 2020 at the Wayback Machine "Im Juli 1846, also nur wenige Monate nach dem Ausbruch des Vulkans, wo ich in diesen Gegenden verweilte, zeigte sich der untere Theil dieses Stromes mit dampfenden Fumarolen übersäet, in denen sich eine solche Menge reiner, zum Theil sehr schön krystallisirter Salmiak sublimirte, dass man dort, trotz der unaufhörlichen Regengüsse, dieses wertvolle Salz zu Hunderten von Pfunden hätte sammeln können." (In July 1846, thus only months after the eruption of the volcano [i.e., Mt. Hekla], where I stayed in this region, the lower part of this [lava] flow appeared studded with steaming fumaroles, in which such a quantity of pure and sometimes very beautifully crystallized ammonium chloride had sublimated that one could have collected there — despite ceaseless downpours — hundreds of pounds of this valuable salt.)
    • Del Campo, Ángel (1912) "Los sublimados blancos del volcán Chinyero (Canarias)" (The white sublimates of the volcano Chinyero in the Canary Islands), Anales de la Sociedad Española de Física y Química, 10 : 431–449.
    • Shipley, J.W. (1919). "Scientific results of the Katmai expeditions of the National Geographic Society: VII. Ammonia and nitrous nitrogen in the rain water of southwestern Alaska". Ohio Journal of Science. 19 (4): 230–234. hdl:1811/2027/V19N04_230.pdf.
    • Sutton et al., p. 599.
  53. ↑ The term for "ammonium chloride" in Arabic is nūshādir or nūshādur, in Sanskrit, navasadaru or navasara, in Chinese, nao sha, and similarly in Armenian and Syriac. Sutton et al., p. 596.
  54. ↑ In De Lapidibus (About Stones), which is attributed to "Pseudo-Aristotle" and which dates from ca. 750–870 A.D., is a brief statement that ammonium chloride was created at the public baths (from the soot of the fires that served to heat the bath waters). Ruska, Julius, Das Steinbuch des Aristoteles mit literargeschichtlichen Untersuchungen nach der arabischen Handschrift der Bibliothèque Nationale [The book of stones of Aristotle with literary-historical investigations into the Arabic manuscript of the Bibliothèque Nationale] (Heidelberg, Germany: Carl Winter, 1912), p. 191. From p. 191 (in Latin): "Et unus lapis est qui vocatur nasciadhor i. liscianada qui fit in balneis." (And there is one stone that is called nasciadhor [i.e., nûshâdur, ammonium chloride] or liscianada that is made [i.e., created] in the baths.) See also: Sutton et al., p. 595.
  55. ↑ The Persian geographer Al-Istakhri (d. 957 A.D.) stated that ammonium chloride was obtained from the soot of camel dung that was burned to heat the public baths in Alexandria. See: (Lippmann, 1919), p. 403. From p. 403: Archived 17 October 2020 at the Wayback Machine Istakhri " … bestätigt das persische Vorkommen … des Nûschâdirs, 'den die Ägypter aus dem Rauche ihrer Bäder haben' [aus dem Rauche des zum Heizen gebräuchlichen getrockneten Kamelmistes], … " (Istakhri confirms the occurrence in Persia … of ammonium chloride (nûshâdir), "which the Egyptians have [obtained] from the smoke of their baths" [i.e., from the smoke of the dried camel dung that's used for heating] … ) See also: Sutton et al., p. 595.
    The production of ammonium chloride from the soot of burned animal dung was reported early in the 18th century by a number of European observers:
    • Sicard, Claude (S.J.), Nouveaux Mémoires de la Compagnie de Jesus dans le Levant [New memoirs of the Jesuits in the Levant], vol. 2 (Paris, France: Nicolas le Clerc, 1717), pp. 96–98. From pp. 96–98: " … nous arrivâmes sur le midy à Desmayer … " ( … we arrived at midday at Desmayer, a town [in the Nile delta] which is inhabited only by Muslims. It is in this place that the most esteemed sal armoniac [i.e., ammonium chloride] in all Egypt is made. This salt is made in ovens, whose top is vented lengthwise and in several places. One places in these vents twenty or thirty round glass bottles, about a foot and a half in diameter, with a neck of half a foot [across]. The bottles are sealed well: filled with soot and a little sea salt, and animal urine. Then one constructs a layer of loam and brick [on top of the oven], which covers everything except the tops of the bottles' necks, which [remain open] to the air. Then a fire is lit in the oven, and it is maintained continually for three days and three nights. The phlegm [i.e., liquid components] of the material contained in the bottles is driven off, and the acid salts and alkalies meet and cling to each other near the neck, [where they] form a white, round mass. The operation being completed, all of the bottles are broken, and these masses are removed, which are called "sal armoniac". It is to be noted that the soot of which I spoke, is produced by the smoke of pats, which is called gellée in Arabic. They [i.e., the pats] are formed from animal manure. Any other smoke is unlikely to condense into sal armoniac.)
    • Geoffroy, Étienne (1720) "Observations sur la nature et la composition du sel ammoniac" Archived 25 July 2020 at the Wayback Machine (Observations on the nature and composition of ammonium chloride), Histoire de l'Académie Royale des Sciences: année MDCCXX, avec les memoires … , pp. 189–191.
    • Lemere (1719) "Adressé à l'Académie sur le sel ammoniac, etc." Archived 26 July 2020 at the Wayback Machine (Address to the [French Royal] Academy [of Sciences] on ammonium chloride, etc.), Histoire de l'Académie Royale des Sciences: année MDCCXX, avec les memoires … , pp. 191–194.
    • (Lemere) (1716) "Observations sur la nature et la composition du sel ammoniac," Archived 26 July 2020 at the Wayback Machine Histoire de l'Académie Royale des Sciences: année MDCCXX, avec les memoires … , pp. 195–207. On p. 202, Lemere states that ammonium chloride can be made by combining ammonium carbonate and hydrochloric acid: "L'on prend de l'esprit ou du sel volatil d'urine; on jette dessus de l'esprit de sel marin, jusqu'à ce qu'il ne se fasse plus de fermentation; on fait évaporer au sable la liqueur, qui, étant séche, fournit un sel salé qui a les mêmes effets que le sel ammoniac." (One takes the spirit or volatile salt of urine [i.e., ammonium carbonate]; one tosses on it spirit of sea salt [i.e., hydrochloric acid], until it no longer makes fermentation [i.e., effervesces]; one evaporates, on a sand [bath], the solution, which, [upon] being dry, furnishes a salty solid which has the same effects as ammonium chloride.)
    • Duhamel du Monceau, Henri-Louis (1735) "Sur le sel ammoniac," Histoire de l'Académie Royale des Sciences: année MDCCXXXV, avec les memoires … , pp. 106–116; 414–434; 483–504. Archived 25 July 2020 at the Wayback Machine
    • Ellis, John (1760). "The method of making sal ammoniac in Egypt; as communicated by Dr. Linnaeus from his pupil Dr. Hasselquist, who had been lately in those parts". Philosophical Transactions of the Royal Society of London. 51: 504–506. doi: 10.1098/rstl.1759.0050 .
    • Beckmann, Johann, Beyträge zur Geschichte der Erfindungen [Contributions to the history of inventions] (Leipzig, Germany: Paul Gotthelf Kummer, 1805), vol. 5, 4. Salmiak, pp. 254–285. English translations: (1) Beckmann, Johann with William Johnston, trans., A History of Inventions and Discoveries, 2nd ed. (London, England: Walker, 1814), vol. 4, pp. 360–384. Archived 20 October 2020 at the Wayback Machine  ; and (2) Beckmann, Johann with William Johnston, trans., A History of Inventions, Discoveries, and Origins, 4th ed. (London, England: Henry G. Bohn, 1846), vol. 2, pp. 396–407. Archived 16 April 2021 at the Wayback Machine
    • Multhauf, Robert P. (1965). "Sal Ammoniac: a case history in industrialization". Technology and Culture. 6 (9): 569–586. doi:10.2307/3101750. JSTOR   3101750. S2CID   113031715.
  56. ↑ This is the dating put forward by Kraus 1942–1943 , vol. I, p. lxv. For its acceptance by other scholars, see the references in Delva 2017 , p. 38, note 14. Notable critics of Kraus' dating are Sezgin 1971 and Nomanul Haq 1994 , pp. 3–47 (cf. Forster 2018).
  57. ↑ Kraus 1942–1943 , vol. II, p. 41.
  58. ↑ Kraus 1942–1943 , vol. II, pp. 41–42 (referring to Stapleton 1905; Ruska 1923a; Ruska 1928). See also Stapleton, Azo & Hidayat Husain 1927 , pp. 338–340.
  59. ↑ "Geberis philosophi perspicacissimi, summa perfectionis magisterii in sua natur ex bibliothecae Vaticanae exemplari". 1542.

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