亚硫酸钙 目录 用途 制备 结构 参见 参考文献 导航菜单10257-55-372878-03-629501-28-81592748329549doi:10.1246/cl.1984.1051USGS Gypsum Statistics and InformationCurrent EU approved additives and their E NumbersSulfites in Foodsdoi:10.1111/j.1600-0536.2012.02135.xdoi:10.1111/j.1365-2222.2009.03362.xdoi:10.1021/es9904235Experimental Investigation and Modeling of a Wet Flue Gas Desulfurization Pilot Plantdoi:10.1021/ie9709446doi:10.1246/bcsj.57.1155doi:10.1246/cl.1983.459doi:10.1246/bcsj.57.593编编

钙化合物亚硫酸盐


亚硫酸盐乾壁石膏E编码亚硫酸盐抗氧化剂过敏木质素硫酸盐制浆法硫化物二硫化铁烟道气酸雨烟囱熟石灰石灰石氧气硫酸根石膏氯化鈣亚硫酸钠X射线晶体学配位数三角反棱柱单晶琼脂



































亚硫酸钙



IUPAC名
Calcium sulfite
别名
E226
识别

CAS号

10257-55-3（无水）  ✓
72878-03-6（四水）  ✗
29501-28-8（半水）  ✗

PubChem

159274

ChemSpider

8329549

SMILES



InChI



InChIKey

GBAOBIBJACZTNA-NUQVWONBAU
性质

化学式

CaSO3

摩尔质量
120.17 g·mol⁻¹
外观
白色固体

熔点
600 °C（873 K）

溶解性（水）
0.0043 g/100 mL, 18℃
危险性

闪点
不可燃
相关物质
其他阴离子

硫酸钙
其他阳离子

亚硫酸钠
若非注明，所有数据均出自一般条件（25 ℃，100 kPa）下。

亚硫酸钙属于亚硫酸盐与钙盐，化学式CaSO3⋅xH2Odisplaystyle ce CaSO3.xH2O。亚硫酸钙有两种已知结晶水合物：半水合亚硫酸钙CaSO3⋅12H2Odisplaystyle ce CaSO3.1/2H2O与四水合亚硫酸钙CaSO3⋅4H2Odisplaystyle ce CaSO3.4H2O[1]，均为白色固体。亚硫酸钙是烟气脱硫（英语：flue-gas desulfurization）的产物之一。




目录





  • 1 用途

    • 1.1 乾壁


    • 1.2 食品添加剂


    • 1.3 木浆生产


    • 1.4 酸抑制剂



  • 2 制备


  • 3 结构


  • 4 参见


  • 5 参考文献




用途



乾壁


在制备乾壁的主要成分石膏的过程中，亚硫酸钙是一种中间产物。一间典型的全新美国房屋含有7公吨石膏[2]。



食品添加剂


亚硫酸钙可用作防腐剂，E编码为E226[3]。与其他亚硫酸盐抗氧化剂类似，亚硫酸钙广泛用于保存葡萄酒、苹果酒、水果汁、罐头水果、蔬菜等[4]。在溶液中，亚硫酸盐是强还原剂，作为除氧剂（英语：oxygen scavenger）起到保存食品的作用。因为部分人群对亚硫酸盐过敏，所以有必要对其进行标注。[5][6]



木浆生产


化学木浆的生产过程是溶解掉木片中的木质素，分离出原本与前者紧密结合的纤维素。在亚硫酸盐制浆法（英语：sulfite process）中，用来分离木质素的盐可以是亚硫酸钙。人们曾经用过亚硫酸钙，但如今镁和钠的亚硫酸盐与亚硫酸氢盐已广泛取代之。另一种制浆法是硫酸盐制浆法，使用的是氢氧化物与硫化物。[7]



酸抑制剂


煤中的二硫化铁在空气中煅烧会生成酸性气体，溶于水形成酸，污染环境：


  • FeS2+3.5O2+H2O→Fe2++2SO42−+2H+displaystyle rm FeS_2+3.5O_2+H_2Orightarrow Fe^2++2SO_4^2-+2H^+

  • 2Fe2++0.5O2+2H+→2Fe3++H2Odisplaystyle rm 2Fe^2++0.5O_2+2H^+rightarrow 2Fe^3++H_2O

  • FeS2+14Fe3++8H2O→15Fe2++16H++2SO42−displaystyle rm FeS_2+14Fe^3++8H_2Orightarrow 15Fe^2++16H^++2SO_4^2-

亚硫酸盐具有还原性，可以除去氧气从而抑制酸的形成。亚硫酸的钠盐、钾盐和铵盐都相对较贵且生产规模较小，而已经大规模生产的亚硫酸钙是该过程中较理想的酸抑制剂。[8]



制备


主条目：烟气脱硫（英语：Flue-gas desulfurization）

通过烟气脱硫（英语：Flue-gas desulfurization）（FGD）可大量制备亚硫酸钙。烟道气指的是煤等化石燃料燃烧后得到的一类副产物，通常包括SO2。人们为了防止酸雨而限制二氧化硫排放，在其他气体从烟囱排出之前，需要除去二氧化硫。比较经济的做法是用熟石灰（Ca(OH)2）或石灰石（CaCO3）处理。


理想状况下，用石灰石除去二氧化硫的反应如下：


SO2 + CaCO3 → CaSO3 + CO2

理想状况下，用熟石灰除去二氧化硫的反应如下：[9][10]


SO2 + Ca(OH)2 → CaSO3 + H2O

如果体系中存在氧气，亚硫酸根就会被氧化为硫酸根，最后可以得到二水合硫酸钙晶体，即石膏[11]。


实验室制法则是令氯化鈣水溶液与亚硫酸钠水溶液反应：


CaCl2 + Na2SO3 → CaSO3 + 2 NaCl


结构


亚硫酸钙的结构已由X射线晶体学检验得出[12]。


半水合亚硫酸钙晶体中，钙的配位数是6，每个钙离子连有五个亚硫酸根的氧原子及一个水分子中的氧原子，六个氧原子组成三角反棱柱的形状。半水合亚硫酸钙晶体热力学较稳定的原因可能是Ca－O键在整个晶体中延展形成网状结构。[13]


四水合亚硫酸钙只在低温下稳定，在室温下会迅速转变为半水合物，因此获得四水合物单晶并分析结构较为困难。不过，使用琼脂制造溶胶环境即可减慢反应物分子的速度，便于结晶，从而制得晶体。[14]四水合亚硫酸钙晶体中钙的配位数同样为6，两个氧原子来自亚硫酸根，四个来自水分子。其热力学不稳定的原因可能是其中的亚硫酸根离子处于无序状态。[15]



参见


  • 亚硫酸盐

  • 亚硫酸镁（英语：Magnesium sulfite）

  • 亚硫酸钠

  • 亚硫酸氢钠

  • 焦亚硫酸钠

  • 坎普登片剂（英语：Campden tablet）


参考文献




  1. ^ Abraham Cohen; Mendel Zangen. Studies On Alkaline Earth Sulfites. Structure and Stability of the New Compound Ca3(SO3)2SO4.12H2O and Its Solid Solution In Calcium Sulfite Tetrahydrate. Chemistry Letters. 1984: 1051–1054. doi:10.1246/cl.1984.1051. 


  2. ^ USGS Gypsum Statistics and Information. USGS. [2017-08-02]. 


  3. ^ Current EU approved additives and their E Numbers. United Kingdom: Food Standards Agency. 2010 [2017-08-04]. 


  4. ^ Sulfites.org. Sulfites in Foods. [2017-08-04]. 


  5. ^ García-Gavín, Juan; Parente, Joana; Goossens, An. Allergic contact dermatitis caused by sodium metabisulfite: a challenging allergen. A case series and literature review. Contact Dermatitis. 2012-11, 67 (5): 260–269. doi:10.1111/j.1600-0536.2012.02135.x. 


  6. ^ Vally, H.; Misso, N. L. A.; Madan, V. Clinical effects of sulphite additives. Clinical & Experimental Allergy. 2009-11, 39 (11): 1643–1651. doi:10.1111/j.1365-2222.2009.03362.x. 


  7. ^ Ropp, Richard. Encyclopedia of the Alkaline Earth Compounds. Elsevier Science Technology. 2013: 145–148. 


  8. ^ Hao, Yueli; Dick, Warren A. Potential Inhibition of Acid Formation in Pyritic Environments Using Calcium Sulfite Byproduct. Environmental Science & Technology. 2000-06, 34 (11): 2288–2292. doi:10.1021/es9904235. 


  9. ^ Hudson, JL. Sulfur Oxidation in Scrubber Systems. University of Virginia. 1980. 


  10. ^ Miller, Bruce. Coal Energy Systems. Elsevier Science Technology. 2004: 294–299. 


  11. ^ Søren Kiil, Michael L. Michelsen and Kim Dam-Johansen. Experimental Investigation and Modeling of a Wet Flue Gas Desulfurization Pilot Plant. Ind. Eng. Chem. Res. 1998, 7 (37): 2792–2806. doi:10.1021/ie9709446. 


  12. ^ Yasue, Tamotsu; Arai, Yasuo. Crystal structure of calcium sulfite. Gypsum & Lime (Jap. Language). 1986, 203: 235–244. 


  13. ^ Matsuno, Takashi; Takayanagi, Hiroaki; Furuhata, Kimio; Koishi, Masumi; Ogura, Haruo. The crystal structure of calcium sulfite hemihydrate. Bulletin of the Chemical Society of Japan. 1984, 57 (2): 1155–1156. doi:10.1246/bcsj.57.1155. 


  14. ^ Matsuno, Takashi; Takayanagi, Hiroaki; Furuhata, Kimio; Koishi, Masumi; Ogura, Haruo. The Crystal Structure of Calcium Sulfite Tetrahydrate. Chemistry Letters. 1983, 12 (4): 459–462. doi:10.1246/cl.1983.459. 


  15. ^ Matsuno, Takashi; Takayanagi, Hiroaki; Furuhata, Kimio; Koishi, Masumi; Ogura, Haruo. The Crystal Structure of Calcium Sulfite Tetrahydrate. Interatomic Distances and Angles. Bulletin of the Chemical Society of Japan. 1984, 57 (2): 593–594. doi:10.1246/bcsj.57.593. 



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亚硫酸盐































































































































































































H2SO3

















He

Li2SO3（俄语：Сульфит лития）

BeSO3











B

C

(NH4)2SO3
NH4HSO3

O

F

Ne

Na2SO3
NaHSO3

MgSO3（英语：Magnesium sulfite）











Al2(SO3)3

Si

P

S

Cl

Ar

K2SO3
KHSO3

CaSO3

Sc

Ti

VO2SO3

CrSO3
Cr2(SO3)3

MnSO3

FeSO3
Fe2(SO3)3

CoSO3

NiSO3（德语：Nickel(II)-sulfit）

Cu2SO3（俄语：Сульфит меди(I)）
Cu3(SO3)2（俄语：Сульфит меди(I,II)）

ZnSO3

Ga

Ge

As

Se

Br

Kr

Rb2SO3（俄语：Сульфит рубидия）
RbHSO3

SrSO3

Y

Zr

Nb

Mo

Tc

Ru

Rh2(SO3)3（俄语：Сульфит родия(III)）

Pd

Ag2SO3（英语：Silver sulfite）

CdSO3（俄语：Сульфит кадмия）

In

Sn

Sb

Te

I

Xe

Cs2SO3
CsHSO3

BaSO3
*

Hf

Ta

W

Re

OsSO3（俄语：Сульфит осмия(II)）

Ir

Pt

Au

Hg2SO3
HgSO3

Tl

PbSO3

Bi

Po

At

Rn

Fr

Ra
**

Rf

Db

Sg

Bh

Hs

Mt

Ds

Rg

Cn

Nh

Fl

Mc

Lv

Ts

Og










↓

















*

La

Ce

Pr

Nd

Pm

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu



**

Ac

Th

Pa

U

Np

Pu

Am

Cm

Bk

Cf

Es

Fm

Md

No

Lr


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