1、Environmental Aquatic ChemistryAcid-base 水體H+的重要性天然水體pH6-9化學(xué)反應(yīng)生物活性酸雨、工業(yè)廢水23天然水體酸堿Most important base: HCO3-Other bases: B(OH)4-, PO43-, NH30, AsO43-, SO42-, CO32-, etc.Most important acid: CO2(aq) or H2CO30Other acids: H4SiO40, NH4+, B(OH)30, H2SO40, CH3COOH0 (acetic), H2C2O40 (oxalic), etc.Rapid Pr

2、ogression of Ocean Acidification in the California Current SystempH8.12pH8.04pH7.924Science, 2012, 337, 220-223541380280碳酸鹽飽和度2.582.271.775Reduced calcification and lack of acclimatization by coral colonies growing in areas of persistent natural acidification6珊瑚蟲(chóng)難以適應(yīng)海洋酸化Effect of Ocean Acidification

3、 on IronAvailability to Marine Phytoplankton7普林斯頓F M M MorelScience，201089Ocean acidification slows nitrogen fixation and growth in the dominant diazotroph Trichodesmium under low-iron conditions10固氮紅海束毛藻固氮紅海束毛藻PNAS, 2012降低鐵攝取降低固氮 Ocean labs probe effects of ocean acidification on ecosystems11超微藻類(lèi)酸化

4、海水中生長(zhǎng)更好硅藻的生長(zhǎng)卻受到了嚴(yán)重影響海膽和海螺的幼蟲(chóng)難以在酸化的海水中生存N AT U R E ， 2 7 J U N E 2 0 1 3 127.2 mg/L1.5mg/L湖泊酸化降低DOC濃度？增加UV-B穿透性DOC的其他影響？13A為有機(jī)陰離子 Science, 1986, 844-847 硫酸根、硝酸根減少的原因？14利用堿度研究碳匯15Science 301, 88-91 (2003)農(nóng)作物耕地面積比森林面積比16Environ. Sci. Technol., 2013, 47 (18), 1030210311酸-堿概念Bronsted概念：質(zhì)子轉(zhuǎn)移Lewis酸堿概念：孤對(duì)電子

5、對(duì)1718酸堿成對(duì)出現(xiàn)H2CO30 + H2O H3O+ + HCO3-NH4+ + H2O H3O+ + NH30CH3COOH0 + H2O H3O+ + CH3COO-H2O + H2O H3O+ + OH-19共軛酸堿對(duì)HCl0, Cl-H2CO30, HCO3-HSO4-, SO42-CH3COOH0, CH3COO-Zn(H2O)62+, Zn(H2O)5(OH)+20酸堿強(qiáng)度Strength: The tendency to donate or accept a proton, i.e., how readily does the substance donate or acce

6、pt a proton? Weak acid has weak proton-donating tendency; a strong acid has a strong proton-donating tendency. Similarly for bases,Cannot define strength in absolute sense. Strength depends on both the acid and base involved in an acid-base reaction.強(qiáng)度與參考水平：水、氨.21離子化強(qiáng)度測(cè)酸強(qiáng)度HA0 + H2O H3O+ + A-orHA0 H+

7、 + A-0HAAHKAThe larger KA, the stronger the acid; the smaller KA, the weaker the acid22pKA AND pH定義pKA = - log KAThus, the larger pKA, the weaker the acid; the smaller pKA, the stronger the acid.Similarly,pH = - log H+pOH = - log OH-pX = - log X堿強(qiáng)度A- + H2O HA0 + OH-20OHAOHHAKBpKB = - log KBThe large

8、r pKB, the weaker the base; the smaller pKB, the stronger the base.物理化學(xué)基礎(chǔ)活度、活度系數(shù)ai =ici24離子強(qiáng)度I、TDS、SC25離子活度系數(shù)26平衡求解圖解法代數(shù)法數(shù)值法 （計(jì)算機(jī)求解）27代數(shù)解質(zhì)量平衡電荷平衡（質(zhì)子平衡）平衡方程28例題初始條件：CaCO3=10-3M;CO2=1.1*10-3M，求溶液組成.確定方程：質(zhì)量平衡、質(zhì)量作用定律選定參考水平H+HCO3-組成形態(tài)初始組成質(zhì)量平衡質(zhì)量作用定律TOTH=H+-OH-+H2CO3-CO32-=-10-3M+1.1*10-3M=0.1*10-3M-14H2CO

9、3=H+HCO3-*106.3若選擇確定參考水平H+CO2例題初始條件：CaCO3=10-3M;CO2=1.1*10-3M;HA=4*10-4M，求溶液組成二氧化碳系統(tǒng)34已知Kh、Ka0，如何求得Ka1？35分布函數(shù)求??？Origin函數(shù)繪制logC-pH圖36具體操作請(qǐng)百度Origin 函數(shù)繪圖功能采用VMINTEQ計(jì)算再畫(huà)圖37CO2=0.1mM,NaCl=0.001M ;NaOH=10-4.5M 二氧化碳等當(dāng)點(diǎn)碳酸根等當(dāng)點(diǎn)碳酸氫根等當(dāng)點(diǎn)38OH-的輸入確實(shí)是輸入-H+近似作圖logC-pHHCO3-和CO32-請(qǐng)按公式自行類(lèi)比分析39密閉系統(tǒng)40純CO2、NaHCO3、 Na2CO3質(zhì)

10、子條件？TOTH41不同濃度近似等當(dāng)點(diǎn)是總碳酸濃度的函數(shù)開(kāi)放系統(tǒng)42ABA、B兩點(diǎn)特點(diǎn)？例題：“純”雨水pH值43參考水平？ H2CO3-H+上一頁(yè)P(yáng)點(diǎn)，pH=5.65堿度44H2PO4-、H2S酸性與H2CO3酸性相當(dāng)酸堿滴定4546無(wú)機(jī)酸度苛性堿度酸中和容量堿中和容量4748Deffeyes圖49CT、堿度、H+例題5051格氏（Gran）滴定52例題53碳酸鹽系統(tǒng)滴定54作業(yè)1552563 Consider a water whose carbonate system is initially at equilibrium with the atmosphere (Pco2=10-3.5

11、 atm). This water contains sulfide:H2ST=2*10-4M and its initial pH is 8.0. What will the final pH of this water be when H2S is lost to the atmosphere?假定大氣中CO2仍與溶液平衡，大氣中硫化氫的分壓為0. 參數(shù)二氧化碳?xì)庖汉嗬?shù)H=10-1.5 atm/(mol/L)，碳酸電離常數(shù)Ka1=10-6.3，Ka2=10-10.3 硫化氫電離常數(shù)Ka1=10-7.0，Ka2=10-13.9 結(jié)果為最終pH8.14.574湖泊的初始條件：堿度Alk=10-3 M；SO42-=10-4 M; pH=7.5現(xiàn)由于硫酸鹽還原菌的作用，將硫酸鹽全部還原為HS-（假定沒(méi)有任何氣體損失）。求硫酸鹽被完全還原后湖水的pH值和堿度和各組