Solubility of Metal Oxides in Deep Eutectic Solvents Based on Choline Chloride]

Solubility of Metal Oxides in Deep Eutectic Solvents Based on Choline Chloride

Andrew P.Abbott,*Glen Capper,David L.Davies,Katy J.McKenzie,and Stephen U.Obi

Chemistry Department,University of Leicester,Leicester,LE17RH,U.K.

The solubility of17commonly available metal oxides in the elemental mass series Ti through Zn have been

determined in three ionic liquids based on choline chloride.The hydrogen bond donors used were urea,malonic

acid,and ethylene glycol.The results obtained are compared with aqueous solutions of HCl and NaCl.Some

correlation is observed between the solubility in the deep eutectic solvents and that in aqueous solutions but some

significant exceptions offer an opportunity for novel solvato-metallurgical processes.

Introduction

Hydrometallurgy is the cornerstone of many metal extraction processes.Aqueous acids or alkalis are predominantly used to dissolve the metal oxides,sulfides,or silicates.Electrowinning and solvent extraction are frequently used to recover and concentrate the metals.A limited number of high-temperature molten salts have also been used extensively for the recovery of refractory metals,such as titanium and aluminum,from their ores.1,2Preliminary studies have shown that ambient temperature ionic liquids have potential as solvents for metal recovery,and the feasibility of these solvents has been demonstrated for the extraction of gold and silver from a mineral matrix3and the recovery of uranium and plutonium from spent nuclear fuel.4 Some work has also been carried out on the electrowinning of metals,principally aluminum,from ionic liquids.5-7However, given the cost and sustainability of many of these imidazolium-based ionic liquids,simpler alternatives will be necessary for large-scale applications.

An alternative approach has been to take simple quaternary ammonium salts and make a complex anion in situ by mixing it with a metal salt,8a hydrated metal salt,9or simple hydrogen bond donors such as amides10and carboxylic acids.11These mixtures form eutectics where the depression of freezing point can be up to200°C.The mixtures have been shown to have similar solvent properties to ionic liquids with discrete anions. To distinguish them,the term deep eutectic solvents(DESs) has been coined.These liquids have high conductivities, viscosities,and surface tensions.The fact that some of the hydrogen bond donors are common bulk commodity chemicals such as urea and oxalic acid gives them the potential for large-scale applications.

The chemistry of metal oxide complexes in low-temperature ionic liquids has received little attention.However,several authors have investigated uranium oxo species in chloroalumi-nate melts.12-14Dai et al.determined the solubility of UO3in imidalozium-based chloroaluminate melts to be e24.58mmol at65°C.12Bell et al.have studied the dissolution of V2O5in (Emim)chloroaluminate ionic liquids.15The oxide was found to be very soluble in the basic melt,0.15g in1g,but also soluble in the neutral melt.The authors report that V2O5reacts with the acidic chloroaluminate melt forming a volatile VOCl3 compound.A key finding in their report is the lack of any solubility of V2O5in neutral ionic liquids such as(Bmim)(BF4) and(Bmim)(CF3SO3).15This signifies the need for a suitably strong coordinating anion to be present for the complexation of the metal oxide to form a soluble species.

We have recently shown that low-temperature chloride eutectics demonstrate high solubilities for a wide range of solutes including metal oxides.10,11In this paper,we report a systematic study of the transition metal oxides of Period4in three different DESs and compare the solubility of the oxides with those found in aqueous solutions.The differences in solubilities are discussed in terms of the metal speciation.

Experimental Section

Choline chloride(HOC2H4N(CH3)3+Cl-)(ChCl)(Aldrich99 %)was recrystallized from absolute ethanol,filtered,and dried under vacuum.Urea and malonic acid(both Aldrich>99%) were dried under vacuum prior to use.Ethylene glycol(EG) (Aldrich99+%)was used as received.The eutectic mixtures were formed by stirring the two components together at100°C until a homogeneous,colorless liquid formed.The molar ratios for the eutectic compositions were found to be2:1for urea or ethylene glycol with choline chloride whereas for malonic acid it is a1:1mixture.Metal solubility was determined by placing 0.1g of the metal oxide(various sources all>98%)in5mL of the DES for2days at50°C.The solution was filtered at 50°C,diluted with0.1N HCl,and analyzed using a JY Ultima 2inductively coupled plasma-atomic emission spectrometer (ICP-AES).Metal solubility measurements for the metal oxides in the aqueous solutions were carried out by stirring0.1g of the metal oxide in5mL each of0.181mol?dm-3NaCl and 3.14mol?dm-3HCl for2days at50°C.For comparison,the acid concentrations in the malonic acid eutectics was4.91 mol?dm-3.

Results and Discussions

Table1shows that for most metal oxides the solubility is in the order HCl>malonic acid>urea>NaCl>ethylene glycol. Higher solubility is observed with the more ionic oxides such as ZnO in an analogous manner to that expected for aqueous acidic solutions.More covalent oxides such as TiO2exhibit negligible solubility.Table1also reports the data for the solubility of a limited number of metal oxides in ChCl:2urea eutectic at70°C,and it can be seen that the trends in metal oxide solubility for the four metal oxides are in proportion to

*Corresponding author.E-mail:andrew.abbott@https://www.sodocs.net/doc/1c2895217.html,.

1280J.Chem.Eng.Data2006,51,1280-1282

10.1021/je060038c CCC:$33.50?2006American Chemical Society

Published on Web06/27/2006

those at 50°C.It is also evident that the solubility exhibits strong temperature dependence particularly for Cu 2O and ZnO.

Figure 1shows the correlation between the solubility of a variety of metal oxides in the three deep eutectic solvents and the solubility in 3.14mol ?dm -3HCl after equilibration of the oxide for 2days at 50°C.The concentration of aqueous acid was chosen to have a similar H +concentration as that in the malonic acid eutectic although it is clearly recognized that the activity of H +is different in the two liquids.The solubility of the oxides in the ChCl:malonic acid eutectic correlate well with those in aqueous HCl.The solubility of the oxides does not however correlate with those in aqueous NaCl solution (not shown),indicating that it is not related purely to the presence of Cl -.The higher solubility of the oxides in HCl and the malonic acid eutectic compared to the other liquids is presum-ably because the protons act as an oxygen acceptor and change the complex formed.

We have previously shown that in the case of ZnO dissolving in the ChCl:2urea eutectic,the complex [ZnClO.(urea)]-forms (i.e.,the oxygen remains bound to the metal).16FAB-MS was carried out on the eutectic samples shown in Table 1.It was only in cases where the metal oxides exhibited high solubility that complexes could be identified;hence,none were identified in the glycol-based liquid.No metal-containing cationic species

were identified,and the anionic species that were identified are listed in Table 2.In the malonic acid-based eutectics CuO,Cu 2O,MnO,and ZnO gave predominantly chlorometalate species of the form MCl x -.This supports the idea that the protons act as an oxygen acceptor.The metals that exhibit higher solubilities tend to have less oxygen attached to the metal center;therefore,it is assumed that the oxygens are more basic in these com-plexes.Most of the complexes identified in Table 2have incom-plete coordination shells,and it is unlikely that this would be the case in a liquid containing strong ligands such as urea.Sig-nals from the acids,amides,and alcohols coordinated to the metals are rarely detected using FAB-MS.It is only with zinc that evidence of amide binding has been observed.In aqueous solutions,water molecules will act as good ligands for the metal centers and will certainly contribute to the high solubility shown in Table 1.

Very few studies have attempted to model the solubility of metal oxides due in part to the issue of speciation.Shin et al.17used modified solution theory to predict the solubility of a range of inorganic compounds in supercritical water.It was shown that the solubility of a solid solute is described by the expression

where ?H 2m and T m are the heats of fusion and the melting

points of the solute,and υand δrepresent the molar volume and solubility parameters.Subscripts 1and 2signify the prop-erties of the solvent and solute,respectively.With the difficulty in identifying all the solute species,prediction of υ2is com-plicated particularly because FAB-MS rarely detects the pres-ence of the hydrogen bond donor in the complex.Solubility parameter data are also unknown in these types of solvents or for these solutes.However,to a first approximation,we will assume that the solutions behave ideally since the molar volume of the solute could be assumed to be constant;hence,eq 1can be expressed as

This is clearly an oversimplification;however,a plot of eq 2for the data in Table 1(where ?H 2m is known)(Figure 2)shows that sufficient correlation is still obtained for the malonic acid eutectic and the HCl solution such that it can be predicted whether the metal oxide will exhibit significant or negligible solubility.

An alternative empirical approach is to assume that the sta-bility of the metal oxide and,hence,its reticence to dissolve is related to the charge density of the metal.Figure 3shows a plot of solubility of the metal oxides in the malonic acid eutectic versus z /r 3where z is the charge on the metal and r is the crystal ionic radius.Relatively good correlation is observed (R )-0.601)with two significant exceptions:V 2O 5and CrO 3.These

Table 1.Solubility of Metal Oxides in Eutectic Mixtures of ChCl with Malonic Acid (1:1),Urea (1:2),and Ethylene Glycol (1:2)

Compared to the Solubilities in Aqueous 0.181mol ?dm -3NaCl and 3.14mol ?dm -3HCl after 2Days a MO malonic acid urea ethylene glycol NaCl HCl urea

TiO 240.50.80.836V 2O 336514814236164686V 2O 55809

4593

131********Cr 2O 34321317CrO 3641510840

712069

2658MnO 6816012028124Mn 2O 3538007.5025962MnO 21140.60.604445FeO 50100.32 2.827053Fe 2O 337600.711.710523 3.7

Fe 3O 42314 6.715 4.522403CoO 362613.61622166260Co 3O 459923018.6 4.0142865NiO 15159.0 3.3610921Cu 2O 183372193940.153********CuO 14008 4.8 4.60.152047234ZnO

16217

1894

469

5.9

63896

90019

a

Solubilities/ppm were measured at 50°C except for last column,which was obtained at 70°

C.

Figure 1.Correlation between the solubility of a variety of metal oxides in three deep eutectic solvents and the solubility in 3.14mol ?dm -3HCl-(aq)after equilibration for 2days at 50°C.

Table https://www.sodocs.net/doc/1c2895217.html,plex Anions Detected Using FAB-MS

hydrogen bond donor metal oxide complex anion urea V 2O 5VO 2Cl 2CrO 3CrO 2Cl 3

ZnO ZnOCl ?urea malonic acid

CrO 3CrO 2Cl 3MnO MnCl 3Cu 2O CuCl 2CuO CuCl 3ZnO

ZnCl 3

ln γ)?H 2m RT (T

T 2

m -1)-υ2RT (δ1-δ2

)(1+υ2υ1)

ln υ2υ1

(1)

ln γ)?H 2m RT ((T T 2

m

)-1)

+constant

(2)

Journal of Chemical and Engineering Data,Vol.51,No.4,20061281

two metals are strong oxidizing agents and could be reduced in the dissolution process;however,this is not likely as the colors of the two solutions are characteristic of the metals in their V and VI oxidation states,respectively.The FAB-MS data show some signals that could arise from species with these oxidation states.

Almost no correlation is observed for the data obtained with the urea and ethylene glycol based eutectics.It is assumed that the major contributory factor is the difference in speciation caused by the protons acting as good oxygen acceptors.Hence for metals with lower oxidation states (I and II),dissolution of the metal oxides tend to produce halo-metalate anions in malonic acid based eutectics.We assume the same will be true of other DESs using carboxylic acid based hydrogen bond donors.11

However,preliminary results using ZnO,CuO,and Fe 3O 4in malonic acid,oxalic acid,and phenylpropionic acid showed 11that the solubility of the oxides could be varied significantly using different carboxylic acids.This could be achieved to such an extent that the relative solubility ratios could be inverted (e.g.,using oxalic acid γ(ZnO)/γ(Fe 2O 3))0.21whereas using phenylpropionic acid γ(ZnO)/γ(Fe 2O 3))33.8).This suggests that the hydrogen bond donor does play a significant part in solvation of the complex,although this cannot be observed using FAB-MS alone.

Conclusions

Malonic acid based DESs exhibit higher solubility than the corresponding liquids based on urea and ethylene glycol.This is thought to originate from the protons acting as good oxygen acceptors and leading to chlorometalate species.Good correla-tion is observed between the solubility of metal oxides in the malonic acid based eutectics and aqueous HCl solutions.

Literature Cited

(1)Fray,D.J.;Chen,G.Z.Mater.Sci.Technol.2004,20,295.

(2)Cherginets,V.Handbook of Sol V ents ;Wypych,G.,Ed.;ChemTec

Publishing:Toronto,2001;pp 1484-1496.

(3)Whitehead,J.A.;Lawrence,G.A.;McCluskey,A.Green Chem.2004,

6,313.

(4)Thied,R.C.;Seddon,K.R.;Pitner,W.R.;Rooney,D.World Patent

WO 99/41752,1999.

(5)Zhang,M.;Kamavaram,V.;Reddy,R.G.Light Metals 2005,583-588.

(6)Wu, B.;Reddy,R.G.;Rogers,R. D.U.S.Patent Application

2002070122.

(7)McCluskey, A.;Lawrance,G. A.;Leitch,S.K.;Owen,M.P.;

Hamilton,I.C.Am.Chem.Soc.Symp.Ser.2002,No.818,199-212.(8)Abbott,A.P.;Capper,G.;Davies,D.L.;Rasheed,R.K.Chem.Eur.

J.2004,10,3769.

(9)Abbott,A.P.;Capper,G.;Davies,D.L.;Rasheed,R.K.Inorg.Chem.

2004,43,3447.

(10)Abbott,A.P.;Capper,G.;Davies,D.L.;Rasheed,R.K.;Tambyrajah,

https://www.sodocs.net/doc/1c2895217.html,mun .2003,70.

(11)Abbott,A.P.;Boothby,D.;Capper,G.;Davies,D.L.;Rasheed,R.

K.J.Am.Chem.Soc.2004,126,9142.

(12)Dai,S.;Shin,Y.S.;Toth,L.M.;Barnes,C.E.Inorg.Chem .1997,

36,4900.

(13)Hopkins,T.A.;Berg,J.M.;Costa,D.A.;Smith,W.H.,Dewey,H.

J.Inorg.Chem .2001,40,1820.

(14)Ryan,D.M.;Riechel,T.L.;Welton,T.J.Electrochem.Soc .2002,

149,A371.

(15)Bell,R.C.;Castleman,A.W.,Jr.;Thorn,D.L.Inorg Chem .1999,

38,5709.

(16)Abbott,A.P.;Capper,G.;Davies,D.L.;Rasheed,R.K.;Shikotra P.

Inorg.Chem.2005,44,6497.

(17)Shin H.Y.;Matsumoto K.;Higashi,H.;Iwai,I.;Arai,Y.J.Supercrit.

Fluids 2001,21,105.

(18)Weast,R.C.,Ed.Handbook of Chemistry and Physics ,55th ed.;CRC

Press:Boca Raton,FL,1974.Received for review January 27,2006.Accepted May 28,2006.The authors thank DTI and KTP for funding this work.

JE060038C

Figure 2.Fit of data in Table 1to eq 2for the solubility of a variety of metal oxides in the malonic acid deep eutectic solvent and the solubility in

3.14mol ?dm -3HCl(aq).?H 2m and T m data obtained from ref

18.

Figure 3.Correlation between the solubility of a variety of metal oxides in the malonic acid deep eutectic solvent and the charge density on the metal.r data obtained from ref 18.

1282Journal of Chemical and Engineering Data,Vol.51,No.4,2006

英语中的比较级与最高级 详解

比较级与最高级 1.as...as 与(not) as(so)...as as...as...句型中，as的词性 第一个as是副词，用在形容词和副词的原级前，常译为“同样地”。第二个as是连词，连接与前面句子结构相同的一个句子(相同部分常省略)，可译为“同..... He is as tall as his brother is (tall) . (后面的as 为连词) 只有在否定句中，第一个as才可换为so 改错: He is so tall as his brother.（X） 2.在比较状语从句中，主句和从句的句式结构一般是相同的 与as...as 句式中第二个as一样，than 也是连词。as和than这两个连词后面的从句的结构与前面的句子大部分情况下结构是相同的，相同部分可以省略。 He picked more apples than she did. 完整的表达为: He picked more apples than she picked apples. 后而的picked apples和前面相同，用did 替代。 He walked as slowly as she did.完整表达为: He walked as slowly as she walked slowly. she后面walked slowly与前面相同，用did替代。

3.谓语的替代 在as和than 引导的比较状语从句中，由于句式同前面 主句相同，为避免重复，常把主句中出现而从句中又出现的动词用do的适当形式来代替。 John speaks German as fluently as Mary does. 4.前后的比较对象应一致 不管后面连词是than 还是as,前后的比较对象应一致。The weather of Beijing is colder than Guangzhou. x than前面比较对象是“天气”，than 后面比较对象是“广州”，不能相比较。应改为: The weather of Bejing is colder than that of Guangzhou. 再如: His handwriting is as good as me. 应改为: His handwriting is as good as mine. 5.可以修饰比较级的词 常用来修饰比较级的词或短语有: Much,even,far,a little,a lot,a bit,by far,rather,any,still,a great deal等。 by far的用法: 用于强调，意为“...得多”“最最...”“显然”等，可修饰形容词或副词的比较级和最高级，通常置于其后，但是若比较级或最高级前有冠词，则可置于其前或其后。

五年级上册成语解释及近义词反义词和造句大全.doc

五年级上册成语解释及近义词反义词和造句大全 囫囵吞枣；【解释】：囫囵：整个儿。把枣整个咽下去，不加咀嚼，不辨味道。比喻对事物不加分析考虑。【近义词】：不求甚解【反义词】融会贯穿[造句];学习不能囫囵吞枣而是要精益求精 不求甚解；bùqiúshènjiě【解释】：甚：专门，极。只求明白个大概，不求完全了解。常指学习或研究不认真、不深入【近义词】：囫囵吞枣【反义词】：精益求精 造句；1；在学习上，我们要理解透彻，不能不求甚解 2；学习科学文化知识要刻苦钻研，深入领会，不能粗枝大叶，不求甚解。 千篇一律；【解释】：一千篇文章都一个样。指文章公式化。也比喻办事按一个格式，专门机械。 【近义词】：千人一面、如出一辙【反义词】：千差万别、形形色色 造句；学生旳作文千篇一律，专门少能有篇与众不同旳，这确实是平常旳练习太少了。 倾盆大雨；qīngpéndàyǔ【解释】：雨大得象盆里旳水直往下倒。形容雨大势急。 【近义词】：大雨如柱、大雨滂沱【反义词】：细雨霏霏牛毛细雨 造句；3月旳天说变就变，瞬间下了一场倾盆大雨。今天下了一场倾盆大雨。 坚决果断；áobùyóuyù：意思；做事果断，专门快拿定了主意，一点都不迟疑，形容态度坚决 近义词；不假思索斩钉截铁反义词；犹豫不决 造句；1看到小朋友落水，司马光坚决果断地搬起石头砸缸。2我坚决果断旳承诺了她旳要求。 饥肠辘辘jīchánglùlù【近义词】：饥不择食【反义词】：丰衣足食 造句；1我放学回家已是饥肠辘辘。2那个饥肠辘辘旳小孩差不多两天没吃饭了 滚瓜烂熟gǔnguālànshóu〔shú)【解释】：象从瓜蔓上掉下来旳瓜那样熟。形容读书或背书流利纯熟。【近义词】：倒背如流【反义词】：半生半熟造句；1、这篇课文我们早已背得滚瓜烂熟了 流光溢彩【liúguāngyìcǎi】解释；光影，满溢旳色彩，形容色彩明媚 造句：国庆节，商场里装饰旳流光溢彩。 津津有味；jīnjīnyǒuwèi解释：兴趣浓厚旳模样。指吃得专门有味道或谈得专门有兴趣。 【近义词】：兴致勃勃有滋有味【反义词】：索然无味、枯燥无味 造句；1今天旳晚餐真丰富，小明吃得津津有味。 天长日久；tiānchángrìjiǔ【解释】：时刻长，生活久。【近义词】：天长地久【反义词】：稍纵即逝 造句：小缺点假如不立即改掉, 天长日久就会变成坏适应 如醉如痴rúzuìrúchī【解释】：形容神态失常，失去自制。【近义词】：如梦如醉【反义词】：恍然大悟造句；这么美妙旳音乐，我听得如醉如痴。 浮想联翩【fúxiǎngliánpiān解释】：浮想：飘浮不定旳想象；联翩：鸟飞旳模样，比喻连续不断。指许许多多旳想象不断涌现出来。【近义词】：思绪万千 造句；1他旳话让人浮想联翩。2:这幅画饱含诗情，使人浮想联翩，神游画外，得到美旳享受。 悲欢离合bēihuānlíhé解释；欢乐、离散、聚会。泛指生活中经历旳各种境遇和由此产生旳各种心情【近义词】：酸甜苦辣、喜怒哀乐【反义词】：平淡无奇 造句；1人一辈子即是悲欢离合,总要笑口常开,我们旳生活才阳光明媚. 牵肠挂肚qiānchángguàdù【解释】：牵：拉。形容十分惦念，放心不下 造句；儿行千里母担忧，母亲总是那个为你牵肠挂肚旳人 如饥似渴rújīsìkě：形容要求专门迫切，仿佛饿了急着要吃饭，渴了急着要喝水一样。 造句；我如饥似渴地一口气读完这篇文章。他对知识旳如饥似渴旳态度造就了他今天旳成功。 不言而喻bùyánéryù【解释】：喻：了解，明白。不用说话就能明白。形容道理专门明显。 【近义词】：显而易见【反义词】：扑朔迷离造句；1珍惜时刻，好好学习，那个道理是不言而喻旳 与众不同；yǔzhòngbùtóng【解释】：跟大伙不一样。 〖近义词〗别出心裁〖反义词〗平淡无奇。造句； 1从他与众不同旳解题思路中，看出他专门聪慧。2他是个与众不同旳小孩

The way常见用法

The way 的用法 Ⅰ常见用法： 1)the way+ that 2)the way + in which（最为正式的用法） 3)the way + 省略（最为自然的用法） 举例：I like the way in which he talks. I like the way that he talks. I like the way he talks. Ⅱ习惯用法： 在当代美国英语中，the way用作为副词的对格，“the way+ 从句”实际上相当于一个状语从句来修饰整个句子。 1)The way =as I am talking to you just the way I’d talk to my own child. He did not do it the way his friends did. Most fruits are naturally sweet and we can eat them just the way they are—all we have to do is to clean and peel them. 2）The way= according to the way/ judging from the way The way you answer the question, you are an excellent student. The way most people look at you, you’d think trash man is a monster. 3）The way =how/ how much No one can imagine the way he missed her. 4）The way =because

人教版(新目标)初中英语形容词与副词的比较级与最高级

人教版（新目标）初中英语形容词与副词的比较级与最高级 （一）规则变化： 1．绝大多数的单音节和少数双音节词，加词尾-er ，-est tall—taller—tallest 2．以不发音的e结尾的单音节词和少数以-le结尾的双音节词只加-r，-st nice—nicer—nicest , able—abler—ablest 3．以一个辅音字母结尾的重读闭音节词或少数双音节词，双写结尾的辅音字母，再加-er，-est big—bigger—biggest 4．以辅音字母加y结尾的双音节词，改y为i再加-er，-est easy—easier—easiest 5．少数以-er，-ow结尾的双音节词末尾加-er，-est clever—cleverer—cleverest, narrow—narrower—narrowest 6．其他双音节词和多音节词，在前面加more，most来构成比较级和最高级 easily—more easily—most easily （二）不规则变化 常见的有： good / well—better—best ; bad (ly)/ ill—worse—worst ; old—older/elder—oldest/eldest many / much—more—most ; little—less—least ; far—farther/further—farthest/furthest

用法： 1．原级比较：as + adj./adv. +as（否定为not so/as + adj./adv. +as）当as… as中间有名字时，采用as + adj. + a + n.或as + many / much + n. This is as good an example as the other is . I can carry as much paper as you can. 表示倍数的词或其他程度副词做修饰语时放在as的前面 This room is twice as big as that one. 倍数+as+adj.+as = 倍数+the +n.+of Your room is twice as larger as mine. = Your room is twice the size of mine. 2．比较级+ than 比较级前可加程度状语much, still, even, far, a lot, a little, three years. five times,20%等 He is three years older than I (am). 表示“（两个中）较……的那个”时，比较级前常加the（后面有名字时前面才能加冠词） He is the taller of the two brothers. / He is taller than his two brothers. Which is larger, Canada or Australia? / Which is the larger country, Canada or Australia? 可用比较级形式表示最高级概念，关键是要用或或否定词等把一事物（或人）与其他同类事物（或人）相分离 He is taller than any other boy / anybody else.

英语中的比较级和最高级

大多数形容词有三种形式,原级,比较级和最高级, 以表示形容词说明的性质在程度上的不同。 形容词的原级: 形容词的原级形式就是词典中出现的形容词的原形。例如: poor tall great glad bad 形容词的比较级和最高级: 形容词的比较级和最高级形式是在形容词的原级形式的基础上变化的。分为规则变化和不规则变化。 规则变化如下: 1) 单音节形容词的比较级和最高级形式是在词尾加 -er 和 -est 构成。 great (原级) (比较级) (最高级) 2) 以 -e 结尾的单音节形容词的比较级和最高级是在词尾加 -r 和 -st 构成。wide (原级) (比较级) (最高级) 3)少数以-y, -er, -ow, -ble结尾的双音节形容词的比较级和最高级是在词尾加 -er 和 -est 构成。 clever(原级) (比较级) (最高级) 4) 以 -y 结尾,但 -y 前是辅音字母的形容词的比较级和最高级是把 -y 去掉,加上 -ier 和-est 构成. happy (原形) (比较级) (最高级) 5) 以一个辅音字母结尾其前面的元音字母发短元音的形容词的比较级和最高级是双写该辅音字母然后再加 -er和-est。 big (原级) (比较级) (最高级) 6) 双音节和多音节形容词的比较级和最高级需用more 和 most 加在形容词前面来构成。 beautiful (原级) (比较级) (比较级) difficult (原级) (最高级) (最高级) 常用的不规则变化的形容词的比较级和最高级: 原级------比较级------最高级 good------better------best many------more------most much------more------most bad------worse------worst far------farther, further------farthest, furthest 形容词前如加 less 和 least 则表示"较不"和"最不 形容词比较级的用法: 形容词的比较级用于两个人或事物的比较,其结构形式如下: 主语+谓语(系动词)+ 形容词比较级+than+ 对比成分。也就是, 含有形容词比较级的主句+than+从句。注意从句常常省去意义上和主句相同的部分, 而只剩下对比的成分。

悲惨的近义词反义词和造句

悲惨的近义词反义词和造句 导读：悲惨的近义词 悲凉(注释:悲哀凄凉：～激越的琴声。) 悲惨的反义词 幸福(注释:个人由于理想的实现或接近而引起的一种内心满足。追求幸福是人们的普遍愿望，但剥削阶级把个人幸福看得高于一切，并把个人幸福建立在被剥削阶级的痛苦之上。无产阶级则把争取广大人民的幸福和实现全人类的解放看作最大的幸福。认为幸福不仅包括物质生活，也包括精神生活;个人幸福依赖集体幸福，集体幸福高于个人幸福;幸福不仅在于享受，而主要在于劳动和创造。) 悲惨造句 1.一个人要发现卓有成效的真理，需要千百个人在失败的探索和悲惨的错误中毁掉自己的生命。 2.贝多芬的童年尽管如是悲惨，他对这个时代和消磨这时代的地方，永远保持着一种温柔而凄凉的回忆。 3.卖火柴的小女孩在大年夜里冻死了，那情景十分悲惨。 4.他相信，他们每个人背后都有一个悲惨的故事。 5.在那次悲惨的经历之后，我深信自己绝对不是那种可以离家很远的人。 6.在人生的海洋上，最痛快的事是独断独航，但最悲惨的却是回头无岸。 7.人生是艰苦的。对不甘于平庸凡俗的人那是一场无日无夜的斗

争，往往是悲惨的、没有光华的、没有幸福的，在孤独与静寂中展开的斗争。……他们只能依靠自己，可是有时连最强的人都不免于在苦难中蹉跎。罗曼·罗兰 8.伟大的心胸，应该表现出这样的气概用笑脸来迎接悲惨的厄运，用百倍的勇气来应付开始的不幸。鲁迅人在逆境里比在在顺境里更能坚强不屈。遇厄运时比交好运时容易保全身心。 9.要抓紧时间赶快生活，因为一场莫名其妙的疾病，或者一个意外的悲惨事件，都会使生命中断。奥斯特洛夫斯基。 10.在我一生中最悲惨的一个时期，我曾经有过那类的想法：去年夏天在我回到这儿附近的地方时，这想法还缠着我;可是只有她自己的亲自说明才能使我再接受这可怕的想法。 11.他们说一个悲惨的故事是悲剧，但一千个这样的故事就只是一个统计了。 12.不要向诱惑屈服，而浪费时间去阅读别人悲惨的详细新闻。 13.那起悲惨的事件深深地铭刻在我的记忆中。 14.伟大的心胸，应该用笑脸来迎接悲惨的厄运，用百倍的勇气来应付一切的不幸。 15.一个人要发现卓有成效的真理，需要千百万个人在失败的探索和悲惨的错误中毁掉自己的生命。门捷列夫 16.生活需要爱，没有爱，那些受灾的人们生活将永远悲惨;生活需要爱，爱就像调味料，使生活这道菜充满滋味;生活需要爱，爱让生活永远充满光明。

The way的用法及其含义(二)

The way的用法及其含义（二） 二、the way在句中的语法作用 the way在句中可以作主语、宾语或表语： 1.作主语 The way you are doing it is completely crazy.你这个干法简直发疯。 The way she puts on that accent really irritates me. 她故意操那种口音的样子实在令我恼火。The way she behaved towards him was utterly ruthless. 她对待他真是无情至极。 Words are important, but the way a person stands, folds his or her arms or moves his or her hands can also give us information about his or her feelings. 言语固然重要,但人的站姿,抱臂的方式和手势也回告诉我们他(她)的情感。 2.作宾语 I hate the way she stared at me.我讨厌她盯我看的样子。 We like the way that her hair hangs down.我们喜欢她的头发笔直地垂下来。 You could tell she was foreign by the way she was dressed. 从她的穿著就可以看出她是外国人。 She could not hide her amusement at the way he was dancing. 她见他跳舞的姿势，忍俊不禁。 3.作表语 This is the way the accident happened.这就是事故如何发生的。 Believe it or not, that's the way it is. 信不信由你, 反正事情就是这样。 That's the way I look at it, too. 我也是这么想。 That was the way minority nationalities were treated in old China. 那就是少数民族在旧中

英语比较级和最高级的用法归纳

英语比较级和最高级的用法归纳 在学习英语过程中，会遇到很多的语法问题，比如比较级和最高级的用法，对于 这些语法你能够掌握吗？下面是小编整理的英语比较级和最高级的用法，欢迎阅读！ 英语比较级和最高级的用法 一、形容词、副词的比较级和最高级的构成规则 1.一般单音节词和少数以-er，-ow结尾的双音节词，比较级在后面加-er，最高级 在后面加-est; (1)单音节词 如：small→smaller→smallest short→shorter→shortest tall→taller→tallest great→greater→greatest (2)双音节词 如：clever→cleverer→cleverest narrow→narrower→narrowest 2.以不发音e结尾的单音节词，比较在原级后加-r，最高级在原级后加-st; 如：large→larger→largest nice→nicer→nicest able→abler→ablest 3.在重读闭音节(即：辅音+元音+辅音)中，先双写末尾的辅音字母，比较级加-er，最高级加-est; 如：big→bigger→biggest hot→hotter→hottest fat→fatter→fattest 4.以“辅音字母+y”结尾的双音节词，把y改为i，比较级加-er，最高级加-est; 如：easy→easier→easiest heavy→heavier→heaviest busy→busier→busiest happy→happier→happiest 5.其他双音节词和多音节词，比较级在前面加more，最高级在前面加most; 如：bea utiful→more beautiful→most beautiful different→more different→most different easily→more easily→most easily 注意：(1)形容词最高级前通常必须用定冠词 the，副词最高级前可不用。 例句： The Sahara is the biggest desert in the world. (2) 形容词most前面没有the，不表示最高级的含义，只表示"非常"。 It is a most important problem. =It is a very important problem.

(完整版)the的用法

定冠词the的用法： 定冠词the与指示代词this ,that同源,有“那(这)个”的意思,但较弱,可以和一个名词连用,来表示某个或某些特定的人或东西. (1)特指双方都明白的人或物 Take the medicine.把药吃了. (2)上文提到过的人或事 He bought a house.他买了幢房子. I've been to the house.我去过那幢房子. (3)指世界上独一无二的事物 the sun ,the sky ,the moon, the earth (4)单数名词连用表示一类事物 the dollar 美元 the fox 狐狸 或与形容词或分词连用,表示一类人 the rich 富人 the living 生者 (5)用在序数词和形容词最高级,及形容词等前面 Where do you live?你住在哪? I live on the second floor.我住在二楼. That's the very thing I've been looking for.那正是我要找的东西. (6)与复数名词连用,指整个群体 They are the teachers of this school.(指全体教师) They are teachers of this school.(指部分教师) (7)表示所有,相当于物主代词,用在表示身体部位的名词前 She caught me by the arm.她抓住了我的手臂. (8)用在某些有普通名词构成的国家名称,机关团体,阶级等专有名词前 the People's Republic of China 中华人民共和国 the United States 美国 (9)用在表示乐器的名词前 She plays the piano.她会弹钢琴. (10)用在姓氏的复数名词之前,表示一家人 the Greens 格林一家人(或格林夫妇) (11)用在惯用语中 in the day, in the morning... the day before yesterday, the next morning... in the sky... in the dark... in the end... on the whole, by the way...

英语比较级和最高级的用法

More than的用法 A. “More than+名词”表示“不仅仅是” 1)Modern science is more than a large amount of information. 2)Jason is more than a lecturer; he is a writer, too. 3) We need more than material wealth to build our country.建设我们国家，不仅仅需要物质财富. B. “More than+数词”含“以上”或“不止”之意，如： 4)I have known David for more than 20 years. 5)Let's carry out the test with more than the sample copy. 6) More than one person has made this suggestion. 不止一人提过这个建议. C. “More than+形容词”等于“很”或“非常”的意思，如： 7)In doing scientific experiments, one must be more than careful with the instruments. 8)I assure you I am more than glad to help you. D. more than + (that)从句，其基本意义是“超过（=over）”，但可译成“简直不”“远非”.难以，完全不能（其后通常连用情态动词can） 9) That is more than I can understand . 那非我所能懂的. 10) That is more than I can tell. 那事我实在不明白。 11) The heat there was more than he could stand. 那儿的炎热程度是他所不能忍受的 此外，“more than”也在一些惯用语中出现，如： more...than 的用法 1. 比……多，比……更 He has more books than me. 他的书比我多。 He is more careful than the others. 他比其他人更仔细。 2. 与其……不如 He is more lucky than clever. 与其说他聪明，不如说他幸运。 He is more （a）scholar than （a）teacher. 与其说他是位教师，不如说他是位学者。 注：该句型主要用于同一个人或物在两个不同性质或特征等方面的比较，其中的比较级必须用加more 的形式，不能用加词尾-er 的形式。 No more than/not more than 1. no more than 的意思是“仅仅”“只有”“最多不超过”，强调少。如： --This test takes no more than thirty minutes. 这个测验只要30分钟。 --The pub was no more than half full. 该酒吧的上座率最多不超过五成。-For thirty years，he had done no more than he （had）needed to. 30年来，他只干了他需要干的工作。 2. not more than 为more than （多于）的否定式，其意为“不多于”“不超过”。如：Not more than 10 guests came to her birthday party. 来参加她的生日宴会的客人不超过十人。 比较： She has no more than three hats. 她只有3顶帽子。（太少了） She has not more than three hats. 她至多有3顶帽子。（也许不到3顶帽子） I have no more than five yuan in my pocket. 我口袋里的钱最多不过5元。（言其少） I have not more than five yuan in my pocket. 我口袋里的钱不多于5元。（也许不到5元） more than, less than 的用法 1. （指数量）不到，不足 It’s less than half an hour’s drive from here. 开车到那里不到半个钟头。 In less than an hour he finished the work. 没要上一个小时，他就完成了工作。 2. 比……（小）少 She eats less than she should. 她吃得比她应该吃的少。 Half the group felt they spent less than average. 半数人觉得他们的花费低于平均水平。 more…than,/no more than/not more than (1)Mr．Li is ________ a professor; he is also a famous scientist． (2)As I had ________ five dollars with me, I couldn’t afford the new jacket then． (3)He had to work at the age of ________ twelve． (4)There were ________ ten chairs in the room．However, the number of the children is twelve． (5)If you tel l your father what you’ve done, he’ll be ________ angry． (6)－What did you think of this novel? －I was disappointed to find it ________ interesting ________ that one． 倍数表达法 1. “倍数+形容词（或副词）的比较级+than+从句”表示“A比B大（长、高、宽等）多少倍” This rope is twice longer than that one.这根绳是那根绳的三倍（比那根绳长两倍）。The car runs twice faster than that truck.这辆小车的速度比那辆卡车快两倍（是那辆卡车的三倍）。 2. “倍数+as+形容词或副词的原级+as+从句”表示“A正好是B的多少倍”。

“the way+从句”结构的意义及用法

“tｈｅwａｙ+从句”结构的意义及用法 首先让我们来看下面这个句子: Ｒead the foｌloｗｉnｇpassagｅａnd talkａbout ｉt wi ｔh your classmaｔes．Try tｏｔeｌl whaｔyｏu thiｎk ｏf Tom aｎd ｏｆｔhe ｗay the chiｌｄrenｔrｅated ｈim. 在这个句子中，ｔhe waｙ是先行词,后面是省略了关系副词that或in whｉch的定语从句。 下面我们将叙述“the ｗaｙ+从句”结构的用法。 1.tｈe wａy之后，引导定语从句的关系词是tｈat而不是hoｗ,因此，<<现代英语惯用法词典＞＞中所给出的下面两个句子是错误的：Ｔhｉs is ｔｈeｗayｈowｉtｈａppened. This is the way how he ａlwａｙs treats me. 2．在正式语体中,thaｔ可被in which所代替;在非正式语体中，ｔhat则往往省略。由此我们得到theｗay后接定语从句时的三种模式：1) tｈe ｗaｙ＋ｔhａt-从句２）the way +ｉn whiｃh－从句3) the ｗay +从句 例如：Ｔｈe way(in whiｃh ，thａt) ｔhｅｓｅｃomｒade ｓloｏｋａｔｐrobｌems is wrong．这些同志看问题的方法

不对。 Ｔｈｅｗａy(that ,ｉn ｗhiｃh)yoｕ’ｒe doinｇit is comple ｔeｌy crａzy.你这么个干法,简直发疯。 Wｅａdmiｒｅd him for thｅｗay ｉｎｗhｉch he fａｃeｓdiｆficultieｓ． Waｌlａｃe ａｎd Ｄarwiｎｇreed ｏn the way ｉｎwhi ｃh ｄｉfｆｅrｅnt forms ｏf life had ｂegｕn.华莱士和达尔文对不同类型的生物是如何起源的持相同的观点。 Thｉs is ｔｈe ｗaｙ（tｈａｔ) hｅdｉd it. I lｉkeｄｔhe waｙ(ｔhat) ｓｈeｏｒganized ｔhe ｍeetｉng． 3.theｗay(tｈat)有时可以与hｏw(作“如何”解）通用。例如： That’s tｈe ｗaｙ(tｈaｔ) shｅspoke. = Tｈat’s how shｅspoke.

初中英语比较级和最高级讲解与练习

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