求助晶体解析中的B类错误

求助晶体解析中的B类错误

本人是新手刚开始接触结晶体，check之后经修改剩下以下三个B类错误，求高人指点！！

PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) 90 Ratio

PLAT222_ALERT_3_B Large Non-Solvent H Uiso(max)/Uiso(min) 96 Ratio

PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C15

第一个的解决方法

SIMU 001 002 38 $C

第二个问题

建议把氢删除用理论加氢， 或者把热参数改成-120000

第三个问题

C15可能要做劈裂处理。

不过，想要得到更加专业的回答，我建议还是下载小木虫APP。不要怕麻烦，APP里面有很多非常专业的资料，还有很多各专业的大牛免费解答各种问题，现在安装，下载资源还免费呢，赶快下载小木虫APP试试吧！

tuer

谢谢哈，由于是菜鸟您的第三个办法“C15可能要做劈裂处理”具体怎么操作不会呀，但是用了您的前两个办法后最后一个B类错误不知道为什么也没了，就剩这一个了：PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) 66 Ratio请问要怎么解决啊？

理论上用了第一个命令之后就能解决这个问题了。 估计你有碳原子无序了。你去LST文件里面看一下有无碳原子劈裂的现象。

找到 Principal mean square atomic displacements U

下面就是原子列表。 有劈裂的就会在该原子后面写着：

may be split into  06258  02177  03140  and  06169  01924  03010

tuer

4楼: Originally posted by cluster8676 at 2012-07-16 01:18:31

理论上用了第一个命令之后就能解决这个问题了。 估计你有碳原子无序了。你去LST文件里面看一下有无碳原子劈裂的现象。

找到 Principal mean square atomic displacements U

下面就是原子列表。 有劈裂的就会在该原

刚看看了没有劈裂啊，碳原子无序要怎么处理啊？

cluster8676

5楼: Originally posted by tuer at 2012-07-15 14:07:41

刚看看了没有劈裂啊，碳原子无序要怎么处理啊？

无序的处理其实不难，但是靠这样也说不清楚。

FVAR  0133620  0782250

PART 1

Ru3    5   0580850  0408430  0805911 21000000  003

PART 2

Ru4    5   0506974  0375615  0647275 -21000000  003

PART 0

要用到上面的part命令。

cluster8676

5楼: Originally posted by tuer at 2012-07-15 14:07:41

刚看看了没有劈裂啊，碳原子无序要怎么处理啊？

你是用的xp么？最好找出是那个C用问题。

tuer

7楼: Originally posted by cluster8676 at 2012-07-16 21:36:48

你是用的xp么？最好找出是那个C用问题。

哦，我是用shelxt解的，从热振动看应该是C16有问题

tuer

6楼: Originally posted by cluster8676 at 2012-07-16 21:36:12

无序的处理其实不难，但是靠这样也说不清楚。

FVAR  0133620  0782250

PART 1

Ru3    5   0580850  0408430  0805911 21000000  003

PART 2

Ru4    5   0506974  0375615  0647275 -21000000  

额。。。这个具体的怎么用啊，直接复制到ins文件里就行吗？太麻烦你拉！！

cluster8676

我建议你先把C16 ISOR一下看看会不会解决问题。

tuer

10楼: Originally posted by cluster8676 at 2012-07-16 22:07:42

我建议你先把C16 ISOR一下看看会不会解决问题。

我已经用了这个命令了：ISOR 001 002 C16，是不是参数设的不对或是解决不了问题？？

cluster8676

你到xp里面输入 info $C就能看出来是哪个C原子有问题了。说不定是别的而不是C16

tuer

12楼: Originally posted by cluster8676 at 2012-07-17 09:22:45

你到xp里面输入 info $C就能看出来是哪个C原子有问题了。说不定是别的而不是C16

看了一下确实是C16有问题啊，它的Ueq比其他的大将近一个数量级呢，这样怎么办啊？

cluster8676

你试试 用EADP命令

在ins文件里面加入 EADP C15 C16 C17 多加几个也无所谓

tuer

14楼: Originally posted by cluster8676 at 2012-07-17 11:32:11

你试试 用EADP命令

在ins文件里面加入 EADP C15 C16 C17 多加几个也无所谓

:cry::cry:我加了EADPC15 C16后问题倒是解决了但又出现了两个新的错误：PLAT230_ALERT_2_B Hirshfeld Test Diff for O8 -- C15 123 su

PLAT413_ALERT_2_B Short Inter XH3 XHn H9 H16A 206 Ang这可怎么办啊？PS:O8 C15 C16是乙醇的结构

Introduction of Programmable controllers

From a simple heritage, these remarkable systems have evolved to not only replace electromechanical devices, but to solve an ever-increasing array of control problems in both process and nonprocess industries By all indications, these microprocessor powered giants will continue to break new ground in the automated factory into the 1990s

HISTORY

In the 1960s, electromechanical devices were the order of the day ass far as control was concerned These devices, commonly known as relays, were being used by the thousands to control many sequential-type manufacturing processes and stand-along machines Many of these relays were in use in the transportation industry, more specifically, the automotive industry These relays used hundreds of wires and their interconnections to effect a control solution The performance of a relay was basically reliable - at least as a single device But the common applications for relay panels called for 300 to 500 or more relays, and the reliability and maintenance issues associated with supporting these panels became a very great challenge Cost became another issue, for in spite of the low cost of the relay itself, the installed cost of the panel could be quite high The total cost including purchased parts, wiring, and installation labor, could range from $30~$50 per relay To make matters worse, the constantly changing needs of a process called for recurring modifications of a control panel With relays, this was a costly prospect, as it was accomplished by a major rewiring effort on the panel In addition these changes were sometimes poorly documented, causing a second-shift maintenance nightmare months later In light of this, it was not uncommon to discard an entire control panel in favor of a new one with the appropriate components wired in a manner suited for the new process Add to this the unpredictable, and potentially high, cost of maintaining these systems as on high-volume motor vehicle production lines, and it became clear that something was needed to improve the control process – to make it more reliable, easier to troubleshoot, and more adaptable to changing control needs

That something, in the late 1960s, was the first programmable controller This first ‘revolutionary’ system wan developed as a specific response to the needs of the major automotive manufacturers in the United States These early controllers, or programmable logic controllers (PLC), represented the first systems that 1 could be used on the factory floor, 2 could have there ‘logic’ changed without extensive rewiring or component changes, and 3 were easy to diagnose and repair when problems occurred

It is interesting to observe the progress that has been made in the past 15 years in the programmable controller area The pioneer products of the late 1960s must have been confusing and frightening to a great number of people For example, what happened to the hardwired and electromechanical devices that maintenance personnel were used to repairing with hand tools They were replaced with ‘computers’ disguised as electronics designed to replace relays Even the programming tools were designed to appear as relay equivalent presentations We have the opportunity now to examine the promise, in retrospect, that the programmable controller brought to manufacturing

All programmable controllers consist of the basic functional blocks shown in Fig 10 1 We’ll examine each block to understand the relationship to the control system First we look at the center, as it is the heart ( or at least the brain ) of the system It consists of a microprocessor, logic memory for the storage of the actual control logic, storage or variable memory for use with data that will ordinarily change as a function power for the processor and memory Next comes the I/O block This function takes the control level signals for the CPU and converts them to voltage and current levels suitable for connection with factory grade sensors and actuators The I/O type can range from digital (discrete or on / off), analog (continuously variable), or a variety of special purpose ‘smart’ I/O which are dedicated to a certain application task The programmer is shown here, but it is normally used only to initially configure and program a system and is not required for the system to operate It is also used in troubleshooting a system, and can prove to be a valuable tool in pinpointing the exact cause of a problem The field devices shown here represent the various sensors and actuators connected to the I/O These are the arms, legs, eyes, and ears of the system, including push buttons, limit switches, proximity switches, photosensors, thermocouples, RTDS, position sensing devices, and bar code reader as input; and pilot lights, display devices, motor starters, DC and AC drives, solenoids, and printers as outputs

No single attempt could cover its rapidly changing scope, but three basic characteristics can be examined to give classify an industrial control device as a programmable controller

(1) Its basic internal operation is to solve logic from the beginning of memory to some specified point, such as end of memory or end of program Once the end is reached, the operation begins again at the beginning of memory This scanning process continues from the time power is supplied to the time it it removed

(2) The programming logic is a form of a relay ladder diagram Normally open, normally closed contacts, and relay coils are used within a format utilizing a left and a right vertical rail Power flow (symbolic positive electron flow) is used to determine which coil or outputs are energized or deenergized

(3) The machine is designed for the industrial environment from its basic concept; this protection is not added at a later date The industrial environment includes unreliable AC power, high temperatures (0 to 60 degree Celsius), extremes of humidity, vibrations, RF noise, and other similar parameters

General application areas

The programmable controller is used in a wide variety of control applications today, many of which were not economically possible just a few years ago This is true for two general reasons: 1 there cost effectiveness (that is, the cost per I/O point) has improved dramatically with the falling prices of microprocessors and related components, and 2 the ability of the controller to solve complex computation and communication tasks has made it possible to use it where a dedicated computer was previously used

Applications for programmable controllers can be categorized in a number of different ways, including general and industrial application categories But it is important to understand the framework in which controllers are presently understood and used so that the full scope of present and future evolution can be examined It is through the power of applications that controllers can be seen in their full light Industrial applications include many in both discrete manufacturing and process industries Automotive industry applications, the genesis of the programmable controller, continue to provide the largest base of opportunity Other industries, such as food processing and utilities, provide current development opportunities

There are five general application areas in which programmable controllers are used A typical installation will use one or more of these integrated to the control system problem The five general areas are explained briefly below

Description

The AT89C51 is a low-power, high-performance CMOS 8-bit microcomputer with 4K bytes of Flash programmable and erasable read only memory (PEROM) The device is manufactured using Atmel’s high-density nonvolatile memory technology and is compatible with the industry-standard MCS-51 instruction set and pinout The on-chip Flash allows the program memory to be reprogrammed in-system or by a conventional nonvolatile memory programmer By combining a versatile 8-bit CPU with Flash on a monolithic chip, the Atmel AT89C51 is a powerful microcomputer which provides a highly-flexible and cost-effective solution to many embedded control applications

Function characteristic

The AT89C51 provides the following standard features: 4K bytes of Flash, 128 bytes of RAM, 32 I/O lines, two 16-bit timer/counters, a five vector two-level interrupt architecture, a full duplex serial port, on-chip oscillator and clock circuitry In addition, the AT89C51 is designed with static logic for operation down to zero frequency and supports two software selectable power saving modes The Idle Mode stops the CPU while allowing the RAM, timer/counters, serial port and interrupt system to continue functioning The Power-down Mode saves the RAM contents but freezes the oscillator disabling all other chip functions until the next hardware reset

Pin Description

VCC：Supply voltage

GND：Ground

Port 0：

Port 0 is an 8-bit open-drain bi-directional I/O port As an output port, each pin can sink eight TTL inputs When 1s are written to port 0 pins, the pins can be used as highimpedance inputsPort 0 may also be configured to be the multiplexed loworder address/data bus during accesses to external program and data memory In this mode P0 has internal pullupsPort 0 also receives the code bytes during Flash programming,and outputs the code bytes during programverification External pullups are required during programverification

Port 1

Port 1 is an 8-bit bi-directional I/O port with internal pullupsThe Port 1 output buffers can sink/source four TTL inputsWhen 1s are written to Port 1 pins they are pulled high by the internal pullups and can be used as inputs As inputs,Port 1 pins that are externally being pulled low will source current (IIL) because of the internal pullupsPort 1 also receives the low-order address bytes during Flash programming and verification

Port 2

Port 2 is an 8-bit bi-directional I/O port with internal pullupsThe Port 2 output buffers can sink/source four TTL inputsWhen 1s are written to Port 2 pins they are pulled high by the internal pullups and can be used as inputs As inputs,Port 2 pins that are externally being pulled low will source current, because of the internal pullupsPort 2 emits the high-order address byte during fetches from external program memory and during accesses to external data memory that use 16-bit addresses In this application, it uses strong internal pullupswhen emitting 1s During accesses to external data memory that use 8-bit addresses, Port 2 emits the contents of the P2 Special Function RegisterPort 2 also receives the high-order address bits and some control signals during Flash programming and verification

Port 3

Port 3 is an 8-bit bi-directional I/O port with internal pullupsThe Port 3 output buffers can sink/source four TTL inputsWhen 1s are written to Port 3 pins they are pulled high by the internal pullups and can be used as inputs As inputs,Port 3 pins that are externally being pulled low will source current (IIL) because of the pullupsPort 3 also serves the functions of various special features of the AT89C51 as listed below:

Port 3 also receives some control signals for Flash programming and verification

RST

Reset input A high on this pin for two machine cycles while the oscillator is running resets the device

ALE/PROG

Address Latch Enable output pulse for latching the low byte of the address during accesses to external memory This pin is also the program pulse input (PROG) during Flash programmingIn normal operation ALE is emitted at a constant rate of 1/6 the oscillator frequency, and may be used for external timing or clocking purposes Note, however, that one ALE pulse is skipped during each access to external Data Memory

If desired, ALE operation can be disabled by setting bit 0 of SFR location 8EH With the bit set, ALE is active only during a MOVX or MOVC instruction Otherwise, the pin is weakly pulled high Setting the ALE-disable bit has no effect if the microcontroller is in external execution mode

PSEN

Program Store Enable is the read strobe to external program memoryWhen the AT89C51 is executing code from external program memory, PSEN is activated twice each machine cycle, except that two PSEN activations are skipped during each access to external data memory

EA/VPP

External Access Enable EA must be strapped to GND in order to enable the device to fetch code from external program memory locations starting at 0000H up to FFFFH Note, however, that if lock bit 1 is programmed, EA will be internally latched on resetEA should be strapped to VCC for internal program executionsThis pin also receives the 12-volt programming enable voltage(VPP) during Flash programming, for parts that require12-volt VPP

XTAL1

Input to the inverting oscillator amplifier and input to the internal clock operating circuit

XTAL2

Output from the inverting oscillator amplifier

Oscillator Characteristics

XTAL1 and XTAL2 are the input and output, respectively,of an inverting amplifier which can be configured for use as an on-chip oscillator, as shown in Figure 1Either a quartz crystal or ceramic resonator may be used To drive the device from an external clock source, XTAL2 should be left unconnected while XTAL1 is driven as shown in Figure 2There are no requirements on the duty cycle of the external clock signal, since the input to the internal clocking circuitry is through a divide-by-two flip-flop, but minimum and maximum voltage high and low time specifications must be observed

Figure 1 Oscillator Connections Figure 2 External Clock Drive Configuration

Idle Mode

In idle mode, the CPU puts itself to sleep while all the onchip peripherals remain active The mode is invoked by software The content of the on-chip RAM and all the special functions registers remain unchanged during this mode The idle mode can be terminated by any enabled interrupt or by a hardware resetIt should be noted that when idle is terminated by a hard ware reset, the device normally resumes program execution,from where it left off, up to two machine cycles before the internal reset algorithm takes control On-chip hardware inhibits access to internal RAM in this event, but access to the port pins is not inhibited To eliminate the possibility of an unexpected write to a port pin when Idle is terminated by reset, the instruction following the one that invokes Idle should not be one that writes to a port pin or to external memory

Power-down Mode

In the power-down mode, the oscillator is stopped, and the instruction that invokes power-down is the last instruction executed The on-chip RAM and Special Function Registers retain their values until the power-down mode is terminated The only exit from power-down is a hardware reset Reset redefines the SFRs but does not change the on-chip RAM The reset should not be activated before VCC is restored to its normal operating level and must be held active long enough to allow the oscillator to restart and stabilize

Program Memory Lock Bits

On the chip are three lock bits which can be left unprogrammed (U) or can be programmed (P) to obtain the additional features listed in the table below

When lock bit 1 is programmed, the logic level at the EA pin is sampled and latched during reset If the device is powered up without a reset, the latch initializes to a random value, and holds that value until reset is activated It is necessary that the latched value of EA be in agreement with the current logic level at that pin in order for the device to function properly

12 Affordable Ways To Good Health

#1 Exercise, and at the very least, just walk

You need to move to burn those calories, to keep your body “oiled” and revving, and your metabolism humming just fine You also don’t need to pay up to get moving Even a brisk walk is considered quite healthy so if you can manage a regular exercise regimen comprised of sustained activity for 30 minutes a day, you’re in good shape

I personally invested in home gym equipment like the kind you find in Bodylastics, Pro-Form and Smooth Fitness But you should weigh the costs of doing so with how much value you get out of any exercise equipment you decide to buy Don’t waste your money on things you don’t use!

#2 Sleep earlier

Those times when I stayed up late or even all night to try to cram even more stuff into an already hectic day are now over The body just won’t let me do those things anymore! And here’s the reason for improving your sleeping habits: your body heals and repairs itself and does its regulatory job while you’re snoozing So give it the rest it deserves to keep you chugging along well the next day A lifetime of bad sleeping habits will no doubt take a toll on you and this is one easy way to avoid getting sick

#3 Consider vitamin supplementation

If you’re not a good eater, you’ll be on your way to depleting your body of required vitamins and minerals Supplements — especially the important ones — are a necessity to help replenish your body’s stores Certain vitamins and minerals are important to prevent certain diseases from occurring and if you’re not getting them from your diet, consider taking a boost from other nutritional sources Check out your local health food store or reputable health food sites like Swanson Health Products or The Vitamin Shoppe for the items you need

I’ve gotten into debates about this with colleagues who believe that you should get all you need from the food you eat, and that would be true if you eat a healthy diet Unfortunately, too many people I know don’t follow healthy diets, and probably have nutritional deficiencies Supplements are there to hopefully help such people get back on track by addressing those gaps The key here is moderation and appropriate treatment

#4 Think twice about joining weight loss programs

They could be a waste of time AND money How do I know Well because there are much cheaper alternatives Not to say that such programs couldn’t work for some people, especially if they’ve already tried everything For those who truly need the extra help, sites like Medifast and eDiets may be helpful

#5 Eat more vegetables, cut down on red meat, caffeine, sugar and salt

Yeah, yeah, yeah…boring You’ve heard this advice before I’m sure — maybe too often And these are some of the hardest things to do, if I say so myself But I am practicing what I’m preaching here How many times have I heard that we should consume several servings of vegetables a day consistently Yech And reduce the amount of red meat we eat Dang What about my favorite foods: coffee, sweets, junk/processed food and french fries Well, I am now reaching middle age and I’m beginning to see people in my life falling into the clutches of diabetes, high blood pressure and heart disease Things are getting too close to home, so I’m changing my diet before I really pay for the junk I consume It’s hard but I’m making it a gradual process and so far, I’m making some strides Don’t forget too that by cutting out the junk, you’re saving money

#6 Never skip breakfast

I used to be one of those breakfast skippers who would pile it on heavily in the evening This is because I wasn’t hungry in the morning but terribly so at night I thought it was just the way some of us were, that it was a natural cycle for some people But in reality, these are bad habits that your body has become accustomed to doing and that needs to be broken I look upon one of my co-workers as an example: he doesn’t have breakfast but eats non-stop when he gets home from work all the way till bedtime Let’s just say this whacks out a body’s rhythm and does a number on glucose levels Needless to say, the guy isn’t exactly in tip top shape nor healthy looking But, I was surprised to learn how actually easy it is to retrain yourself into breaking those bad eating habits and found that my eating cycles are now better regulated resulting in less food consumed each day and overall improved health

#7 Never eat an incomplete meal

I’ve actually made an investment in my health by seeing a nutritionist on occasion to correct my lifelong wrongs when it came to food and diet Among the simplest, yet most valuable information I picked up (which I’m sure you can learn from other sources) is this: never eat an incomplete meal What does this mean This means that each meal we take should always contain all three basic food groups: carbohydrates, healthy fats and protein, because your body needs all three food elements to absorb properly and most efficiently in your body

#8 Don’t let yourself go hungry

It’s weird but I also learned that if you can be proactive and anticipate when you’ll be hungry, and actually eat something before you do, you’ll eat less, and better If you eat right after you find yourself starving, you’ll end up devouring more than you need to By the same token, if you eat slowly and chew your food well, you’ll be able to control your food consumption better

#9 Don’t stress out

Those health experts keep saying it: toxins are all over our environment invading our systems, but some of these things are just not within our control I’ll guarantee you’ll be breathing second hand smoke, car fumes and smog every time you go out of the house and enter a city What about chemical agents in our hair spray, pesticide in our food or toxic materials hiding in old buildings where you work You can’t escape these things Well, one thing you can control is how stressed you are Stress impacts your body in the same way terrible toxins do, so do your best to avoid it

#10 Wash your hands often

Avoid getting sick by washing your hands often Unless you don’t mind catching a bout of the cold or flu once in a while, or being a little dirty, which is actually good for you I’ve had interesting conversations with a co-worker who advocates germs and infections as the way to better health in the long run That’s because your body builds up its defenses and immune system by falling ill But as a parent of a school-aged child I still don’t like catching annoying colds, plus getting sick often doesn’t seem to have improved my health

#11 Toss the vices

The spirit is willing, but the flesh is weak It’s something you just cannot “nag” someone to do, since many a time, they’d rather take the chance and possibly face the consequences of their long term habits at a later time After all, the reasoning goes, you can just as easily get run over by a bus than pick up health problems from some random vice Still, you know the drill And one other sticking point is how much you could actually save by giving up these extras

#12 Visit your doctor for annual tests

Those annual tests are covered by your health insurance or can be performed through free or low cost programs Routine tests can catch problems early on before they develop into real trouble later Don’t let it grow into a big issue that costs a lot to deal with

So just remember that an ounce of prevention is worth a pound of cure!

气相色谱法

方法提要

地下水和地表水样品一般结合吹扫捕集、共沸蒸馏、真空蒸馏、分液漏斗液-液萃取、连续液-液分配提取或其他适当的富集方法 (如固相萃取法等) 富集后导入 GC/FID测定，以获得适当的定量限。

柴油范围有机物 (DROs) 可以用适当的溶剂萃取法处理。

汽油范围有机物 (GROs) 可以通过吹扫捕集、自动顶空、真空蒸馏或别的适当技术导入 GC/FID。

可以使用填充柱或毛细管柱分析和检测单独的非卤代烃化合物，通过改变色谱条件以达到适当的分离特性。

熔融石英毛细管柱用于分析石油烃类。

方法用于检测各种挥发性和半挥发性非卤代烃有机化合物，可定量检测的化合物见表8255。

表8255 可检测化合物

续表

注:b为用此技术有足够的响应;d为通过共沸蒸馏法浓缩;ht为仅在80℃使用此方法净化分析物;

I为该技术不适用于这种分析物;pp为低的净化效率，导致高的EQLs;NA为不可用。

本法可用于分析石油烃，包括汽油类有机物(GROs)和柴油类有机物(DROs)。GROs指C6～C10范围链烃，沸程范围大概为60～170℃;DROs指C10～C28范围链烃，沸程范围大概为170～430℃。由于蒸发和生物降解等环境行为，特有的燃料种类或者多种燃料中的某种燃料的识别是很复杂的，有时需用其他更适合的方法识别GROs和DROs。

本法也可作为易挥发和半挥发有机物的筛选工具，获得半定量的数据，以防止用GC-MS定量分析时过负荷。可用自动化顶空法进样，如果已用溶剂提取法处理试样，则可采用直接进样，在这种情况下可以使用单点校正法。

仪器和装置

气相色谱仪 检测器-火焰离子化检测器 (FID)

吹扫捕集导入装置。

推荐气相色谱柱:

1) 8ft × 01in ID 不锈钢或玻璃柱，填充表面有 1% sp-1000 的 Carbopack-B 60 /80目，或相当规格。

2) 6ft × 01in ID 不锈钢或玻璃柱，填充表面有正辛烷的 Porasil-C 100 /120 目 (带有化学结合相的多孔硅胶珠) ，或相当规格。

3) 30m × 053mm ID 熔融石英的毛细管柱，结合有 DB-Wax (或相当物质) ，膜厚 1μm。

4) 30m × 053mm ID 熔融石英的毛细管柱，化学结合 5% 聚甲基硅氧烷 (DB-5，SPB-5，RTx，或相当物质) ，膜厚 15μm。

毛细管柱是用来分析石油烃的，也可使用确认特性数据 (如色谱分离和 MDLs) 的其他色谱柱 (如 025～032mm ID 毛细管色谱柱) 。

粗径毛细管柱前应当接 1/4in 的进样口并且有针对于此柱子使用的特殊钝化衬垫设计。

5mL Luer-lok 玻璃注射器。

5mL 气密的、有针对于易挥发分析物关闭阀的注射器。

微型注射器 如 10μL 和 25μL 且带有 0006in ID 的针 (Hamilton 702N 或相当规格)和 100μL 注射器。

试剂

试剂水 该方法中所有提到的水均指无有机物水。

甲醇 农残级。

石油或柴油 工业燃料 (燃料中低沸点的成分很快蒸发) 。

烷烃标准物质 包括一系列相应的正构烷烃类化合物，用来确立它们的保留时间(如用 C10～ C32作柴油的标准) 。

标准储备溶液 由纯的标准物质制备或者是购买有保证的溶液。当甲醇为目标分析物或在样品前处理阶段使用共沸蒸馏法时，标准溶液均不可用甲醇配制。标准溶液必须每隔6 个月重配一次，或发现问题时重配。

标准中间溶液 可以是单标或所有组分的混合物，用作进一步配制校准系列溶液或监控标准溶液。为防止易挥发组分的损失，应当存放在有最小液面上空的容器内并经常检测其降解和蒸发情况。

校准系列溶液 最少配制 5 个浓度水平的校准溶液系列，用标准中间溶液配制，可用水配制 (吹扫捕集法或直接进样) 或用二氯甲烷配制 (溶剂进样) 。其中一个校准溶液的浓度应当等于或低于定量限，其余标样的浓度应当与真实样品的预计浓度范围符合或者应当在气相色谱规定的工作范围。每一个标样都应当包含用这个方法检测的所有分析物。易挥发的有机物标样用纯水配制。

配制精密度高的标准水溶液的注意事项:

不要将超过 20μL 的甲醇为溶剂的标样注入 100mL 水中。

使用25μL Hamilton 702N 微量注射器或与之相当规格的注射器，如取甲醇为溶剂的标准时，针的几何形状的变化将会影响移入水中标样体积的可重现性。

要快速地将初级标样注入已填充溶剂的容量瓶中，注射后尽可能快地将针头移开。

混合稀释的标样时仅需上下颠倒容量瓶 3 次。

吸取容量瓶大肚部分的标准溶液 (不要用任何瓶颈处的溶液) 。

当需要稀释易挥发的有机物标样时，不要用移液管稀释标样或转移样品和含水标样。

用于吹扫捕集分析的水溶液标准不稳定，所以 1h 之后则应当丢弃，除非将标样注满小瓶密闭保存才可超过 1h 使用，最多不超过 24h。水溶液标样用作共沸蒸馏时最多可以存放 1 周，存放时将标样置于有聚四氟乙烯 (PTFE) 螺帽的密闭瓶子中，具有最小液面上空，4℃避光保存。

内标溶液 选定一个或多个内标物，所选定的内标物和分析物在分析过程中的行为应当相似，内标物应不受基质干扰的影响。一般没有单一内标物能满足所有限定条件。当用共沸蒸馏方法处理样品时，推荐使用下列内标: 2-氯代丙烯腈、六氟代 -2-丙醇和六氟代 -2-甲基 -2-丙醇。

替代物标准溶液 在处理每个试样、标准和空白时，添加一个或两个不受干扰的替代化合物，以此来监控分析系统的功能和方法的有效性。

样品的采集，保存和处理

1) 挥发性有机物采样参见 8291 样品采集、保存和制备部分。

2) 半挥发性有机物。测定半挥发性有机物用的采样容器应用肥皂和水洗涤，然后再用甲醇 (或异丙醇) 冲洗。样品容器应是由玻璃或聚四氟乙烯制的，并带有聚四氟乙烯(或溶剂冲洗过的铝箔) 衬垫的螺旋盖。强酸性或强碱性样品会和铝箔反应导致样品被污染。不能用塑料容器或盖来贮存样品，因为来自塑料中的酞酸酯和其他碳氢化合物可能污染样品。应小心填装样品容器，以防止所采集样品的任何部分接触到采样者的手套而引起污染。不能在有尾气存在的地方采集或贮存样品，如果样品与采样器接触 (例如，使用自动采样器) ，用试剂水通过采样器并用作现场空白。

分析步骤

1) 试样导入方法。所有内标、替代物和基质添加都要在试样导入 GC / FID 系统前添加到样品中。

a直接进样。直接用注射器将试样注射到 GC 口内。

易挥发有机物 ［包含汽油范围有机物 (GROs) ］: 将含有高浓度分析物的水样、共沸蒸馏不清洁的低沸点有机物处理得到的含水浓缩物或有机溶剂废弃物注射入 GC 进样口。直接注射未浓缩的水样有很多限制，易挥发物的毒性 (TC) 达到法定限度或浓度超过10000μg /L 时才可许采用该法检测。如果酒精浓度 > 24% ，也可以应用直接进样检测水样的可燃性。

半挥发性有机物 ［包含柴油范围有机物 (DROs) ］: 将用分液漏斗液-液萃取或连续液-液分配提取处理得到的水样的萃取物注射入 GC 进样口。

b吹扫捕集。

吹扫捕集分析水样。也可用甲醇(和其他易与水混合的溶剂)提取含油水样中待测物，随后用吹扫捕集法测定。通常在室温下对水样进行吹扫捕集。有时需要将水样加热吹扫以降低检测限;然而，25mL的试样在大多数情况下都能提供足够的灵敏度。

c真空蒸馏。可用于将水样、固体样或组织样品中易挥发有机物导入GC/FID系统。

d自动静态顶空。可用于将水样、固体样或组织样品中易挥发有机物导入GC/FID系统。

2)推荐色谱条件。

柱1:载气(He)流速40mL/min。温度程序，初始温度45℃，保持3min，以8℃/min的速度升温，从45℃升温至220℃，最终温度220℃，保持5min。

柱2:载气(He)流速40mL/min。温度程序，初始温度50℃，保持3min，以6℃/min的速度升温，从50℃升温至170℃，保持4min。

柱3:载气(He)流速15mL/min。温度程序，初始温度45℃，保持4min，以12℃/min的速度升温，从45℃升温至220℃，保持3min。

柱4(DROS):载气(He)流速5～7mL/min。尾吹气(He)流速30mL/min。进样口温度200℃，检测器温度340℃。温度程序，初始温度45℃，保持3min，以12℃/min的速度升温，从45℃升温至275℃，保持12min。

3)初始校准。对于每一种样品导入方法，建立气相色谱操作的参数，绘制相应的不同标准曲线。对于没有净化的易挥发物推荐使用内标法，内标物为六氟-2-丙醇、六氟-2-甲基-2-丙醇和2-氯丙烯腈。

a分析单一组分分析物的外标校准步骤。对于每一个目标化合物和替代物，最少准备5个不同浓度的校准标准溶液。分取一种或几种标准储备液于容量瓶中，用适宜的溶剂稀释至刻度。其中某个外标溶液的浓度应该小于或等于要求的定量限(以预处理方法中确定的最终体积内未稀释的浓度为基础)，其他校准标样的浓度应当与真实样品的预期浓度范围相对应，或者由检测器的工作范围来确定。

用与实际试样导入气相色谱相同的技术导入每个校准溶液。将峰高或峰面积响应值对进样量列表。计算每个组分分析物的校准因子(CF)。

CF=标准溶液中化合物的峰面积(或峰高)/化合物注入质量(ng)

bDROs和GROs的外标校准步骤。用来校准的响应值表现为DROs和GROs保留时间范围内的色谱图全面积，包括含在单一峰内的未分开的复杂混合物。

对于每一类型燃料，最少准备5个不同浓度水平的校准溶液。分取一种或几种标准储备液于容量瓶中，用适宜的溶剂稀释至刻度。一种外标的浓度应该小于或等于要求的定量限(以预处理方法中确定的最终体积内未稀释的浓度为基础)。其他校准溶液的浓度应当与真实试样的预期浓度范围相对应，或者由检测器的工作范围来定。

`注意:只要有可能，应当用污染取样现场的特定燃料来配制校准溶液(例如，被怀疑已漏的油桶内残余的燃料样品)。如果这样的样品不易获得或不知晓，则使用最近购买的商用燃料。定性筛选注射和GC分析也许能识别未知燃料。

用与实际试样相同的气相色谱导入技术导入每个校准溶液。计算每种类型燃料的校准因子(CF):

CF=保留时间范围内的总面积/化合物注入质量(ng)

4)校准线性。在整个工作范围内，如果校准因子的相对标准偏差(RSD，%)小于20%，此有机物的线性可以被采取，而且可以用平均校准因子取代校准曲线。

在整个工作范围内，RSD(%)如果大于20%，此有机物的线性就不能被采用。可使用非线性等其他校准选择。

保留时间窗口。单一组分目标分析物以保留时间窗口为基础鉴别。DROs和GROs以每个类型燃料中的特征组分的保留时间范围为基础进行鉴别。

在建立保留时间窗口之前，一定要确定色谱系统的功能是可靠的;并且已经对被分析的试样混合物中的目标分析物和替代物的操作参数进行了优化。

在初始校准中已定义了GROs的保留时间范围。两个特殊的汽油组分(2-甲基戊烷和1，2，4-三甲基苯)可以用来建立这个范围。保留时间范围的计算基础为:保留时间窗口最低限为第一个流出组分，保留时间窗口最高限为最后一个流出组分。

在初始校准中已定义了DROs的保留时间范围。此范围的建立基础为C10和C28烷烃的保留时间。保留时间范围的计算基础为:保留时间窗口最低限为第一个流出组分，保留时间窗口最高限为最后一个流出组分。

5)校准持续确认。校准曲线和保留时间必须在每12h换班开始时检验，这是最低要求。当单一的目标分析物被分析时，检验可以通过测量含有所有目标分析物和替代物的一个或多个校准溶液(通常是中间浓度的)来完成。当石油烃被分析时，检验可以通过测量燃料标准和烃的保留时间标准来完成。强烈建议12h内不断追加分析检验标准溶液，尤其对于含有可见浓度浸油物质的试样。

如果对于任何分析物的响应值与初始校准所获得的响应值相差在±15%以内，则初始校准被认为是有效的，可以继续将初始校准所测得的CF值或RF值用于试样定量(若分析时使用共沸蒸馏作为试样导入技术，D可达±20%)。如果分析物的响应值与初始响应值相差±15%以上(共沸蒸馏为±20%)，必须采取校正措施重新恢复系统或者针对此化合物绘制新校准曲线。

在校准检验分析中，所有目标分析物和替代物或正构烷烃都应当符合先前已测定的保留时间窗口。如果任何分析物的保留时间不在±3σ窗口之内，必须采用重建系统的校正行为或者针对此化合物准备新的校准曲线。

溶剂空白和任何方法空白应当在校准检验分析时运行，以验证实验室污染没有造成假阳性。

6)气相色谱分析。试样分析顺序，以校准检验开始，接着是试样提取分析。强烈推荐12h内不断追加分析检验标样，尤其是含有可见浓度浸油物质的试样。在一批分析结束时再分析一个检验标样。当一批试样已被注射入气谱或者当保留时间或D(%)质量控制标准超标，顺序结束。如果标准超标，在重新标定和进行试样分析之前，检查气相色谱系统。所有采用外标校准的分析必须包括数据质量分析(例如，校准和保留时间校准)。所有超过质控标准的标样浓度和超过校准曲线范围的试样都必须重新分析。

试样分析与校准使用的仪器条件应相同。当将吹扫捕集试样导入时，打开样品小瓶或从封闭的小瓶中取出一部分试样(于是产生顶空)都将危及易挥发试样的分析。因此，推荐准备两个平行试样进行吹扫捕集分析。如果第一个试样的分析不成功或者结果超过了方法校准范围，第二个试样可以安全贮存24h用来重新分析或稀释。共沸蒸馏所得的分馏物可分成两部分并且在分析前将其共置于4℃环境中。推荐在蒸馏24h内分析蒸馏液(最长不超过7d)。

如果试样响应超过初始校准浓度范围，必须分析稀释的试样。对于含有易挥发有机物的水样，用来稀释的必须是试样的备份，即已密封和贮存准备使用和再分析的试样。稀释萃取液使所有的峰处于合适的尺寸，因为当色谱峰不合尺寸时重叠峰可能不很明显。为保证超过100倍范围的所有峰值都在合适的尺寸范围内，计算机对色谱峰进行处理，重新给出色谱图。只要未超过校准限定都可操作。当重叠峰导致峰面积积分错误时，推荐测量峰高而不用峰面积积分。

当试样萃取物中的一个峰落入每日保留时间窗口时，单一组分分析可被暂时辨认。需要用第二根色谱柱或GC/MS证实。由于火焰离子化检测器是非选择性的，所以强烈推荐使用GC/MS定性单一组分分析物，除非可获得支持定性的历史数据。

对于石油烃分析，一般不需要第二根色谱柱证实。然而，如果分析有干扰，则要求使用第二根GC柱分析确认，也要确认样品烃落在初始校准所建立的保留时间范围内。

注意:燃料尤其是汽油，由于它们固有的挥发性致使鉴定是复杂的。燃料的早期洗提化合物显现出很强的挥发性，取样后若不马上用塞子塞住，极易风蚀。在汽油的色谱图中，汽油极易挥发的部分组成了50%的重要峰面积。这一小部分很少能在环境样品或低浓度的有关汽油残余物色谱图中显现。

每12h通过复测空白、标准和重份试样以检查全分析系统的状态。需校正严重的拖尾峰，峰拖尾问题经常由色谱柱的活性部位、气相色谱的冷部位、检测器的操作或者系统的泄露导致。

7)计算。试样中每个分析物的浓度可通过吹扫或注射标准的量计算。标准的量可以用校准曲线或从初始曲线获得的CF或RF得到色谱峰的响应值计算。

尽管汽油和柴油含有的多种混合物能在GC/FID色谱图中有较好的分辨率，但两种燃料都含有太多其他组分，这些组分不能被色谱分辨。这些未分辨的复杂混合物导致色谱图中的“巅峰值”，形成了这些燃料的特征。另外，尽管分离的色谱峰在定性特定的燃料类型时很重要，但未分离的色谱峰的峰面积可能占总响应面积的大部分。

为了分析DROs，将C10和C28的所有峰面积加和。这个面积由C10和C28保留时间范围内所有基线凸起部分构成。

分析DROs使用的气相色谱条件会导致严重的柱流失，同时导致基线上升，所以应该在测DROs气相色谱图的面积时适当的减去柱流失。在分析试样中的DROs时，每12h换班时分析二氯甲烷空白，用测定试样的方式测量该色谱图峰面积。先通过DROs保留时间的范围制定水平的基线，然后将该面积值从已测量的试样面积中减去，所得面积之差按下式计算出DROs的浓度。

a外标法校准-线性校准模型:

岩石矿物分析第四分册资源与环境调查分析技术

式中:ρS为试样中目标分析物的浓度，μg/L或ng/mL;AS为试样中分析物的峰面积(或峰高);Vt为试样浓缩液的总体积(μL)，吹扫-捕集法分析中不存在Vt值，因此设定为1;CF为为初始校准的校准因子，每ng的面积值(或峰高);D为试样或试样提取液分析前的稀释因子，试样品没有稀释时D=1，量纲为一;Vi为提取液进样体积(μL)，通常水样和校准标准品的进样体积应该相同，对于吹扫-捕集分析法不存在Vi，因此取值为1;如果计算校准因子时使用了浓度单位，则在此方程式中不使用Vi;VS为水样或吹扫体积，mL。

如果使用吹扫-捕集方法，样品的甲醇提取液加入到了水中进行测定。

如果使用不通过原点的线性校准，可以用最小二乘法做线性回归，得到回归方程。根据面积响应值(y)、斜率(a)和截距(b)计算测定溶液中分析物的浓度，然后换算为原样中的浓度。

对于吹扫-捕集分析法，若吹扫进样前未对试样进行稀释，则进入系统的样品中分析物的浓度与原始浓度相同。

b内标法校准-线性校准。水样中每个分析物的浓度按下式计算:

岩石矿物分析第四分册资源与环境调查分析技术

式中:ρS为试样中目标分析物的浓度，μg/L或ng/mL;ρiS为测定液中内标物的浓度，μg/L或ng/mL;AS为试样中分析物的峰面积(或峰高);AiS为内标物的峰面积(或峰高);Vt为试样浓缩液的总体积(μL)，吹扫-捕集法分析中不存在Vt值，因此设定为1;CF为为初始校准的校准因子，每ng的面积值(或峰高);D为试样或试样提取液分析前的稀释因子，如果试样品没有稀释，D=1，量纲为一;Vi为提取液进样体积(μL)，通常试样和校准标准的进样体积相同，对于吹扫-捕集法不存在Vi，故取值为1;如果计算校准因子时使用了浓度单位，则在此方程式中不使用Vi;RF为初始校准的平均响应因子，与外标法的校准因子不同，响应因子量纲为一;VS为水样或吹扫体积，mL。

c非线性校准曲线的计算。当使用非线性曲线校准时，非线性方程必须变形后，求解提取液或吹扫体积中分析物浓度，然后将提取液中分析物浓度换算成试样中分析物的浓度。

为了分析DROs，将分布在2-甲基戊烷和1，2，4-三甲基苯之间所有的峰面值相加，使用上述方程式计算GROs浓度。GROs分析中通常不需要减去柱流失。

计算公式涵盖了外标校准和内标校准、直线校准曲线和非直线校准曲线。

8)筛选。为了减少GC/MS分析高度污染样品造成的仪器停工期，可用本法的单点校准进行筛选。

与GC/MS连接的进样设备配置同样可用于GC/FID或其他配置。

建立起稳定的系统响应和稳定的色谱保留时间，分析GC/MS校准标准的最高点。

分析水样或水样萃取液时，当目标待测物浓度超过校准曲线高限时，且在相同保留时间没有其他化合物流出，比较试样和最高浓度标准中分析物的峰高，计算试样中分析物的浓度。然而与GC/MS系统相比，FID对卤化物反应不太灵敏，因此上述比较方法并不绝对正确。

为了确定仪器响应和气相色谱保留时间的稳定性，最高点标准应该最少每隔12h分析一次，但是对于筛选不要求做质量检测。

9)仪器维护。注入废弃物试样的萃取液通常会在注射口区域、分流器(分流进样时)和色谱柱头留有高沸点的剩余物，该剩余物影响一些气相色谱分析性能(例如，残余物峰值、保留时间变化、分析物降解等)，因此仪器维护非常重要。分流器中残余物累积可能迫使气流拐弯，由此改变分流比。如果这种情况在分析时发生，定量数据有可能不准确。适当的清理技术使问题最小化，质量检测设备将显示何时需要仪器维护。

推荐气相色谱仪维护。

分流装置的连接:连接双柱可使用压力适应Y形的玻璃分流装置或者是Y形熔凝石英的连接器，清洁并将分流装置脱活或更换用洁净脱活的分流器。切除柱子靠近进样口一端的几英寸(最多1英尺)。根据生产商的说明，拆下柱子和用溶剂反向冲洗进样口。如果这些步骤不能消除降解问题，有必要对进样口金属主体进行脱活处理或更换柱子。

柱子冲洗:柱子应该用几倍柱体积的适当溶剂冲洗。极性和非极性溶剂都可使用，根据样品残余物的性质决定，第一次用水冲洗，接着用甲醇和丙酮，最后用二氯甲烷冲洗。有时只用二氯甲烷冲洗。为了使固定相中的试样残留物转入溶剂，柱子内应该注满二氯甲烷，保持过夜;然后用新鲜的二氯甲烷冲洗柱子，再排干，室温下用超纯的氮气流干燥柱子。

质量控制

在每批试样分析过程中都应包括方法空白、基质添加、重复样和质量控制样。

如果估计试样中含有目标分析物，要使用一个基质添加样和一个未添加基质的实际试样重复分析。若估计试样中不含有目标分析物，则应使用一个基质添加样和一个基质添加重复样。

分析每批试样时，都应分析一个实验室质量控制样(LCS)。LCS含有相似于试样的基质成分，与试样基质具有相同质量或体积。该LCS用相同的待测化合物、同样浓度添加作为基质添加样。当添加基质分析结果显示潜在的问题由试样基质本身产生时，LCS结果可用来校验实验室用的清洁基质的分析结果。

应评价每个试样中的替代物回收率。

方法性能

水基质中使用共沸蒸馏的挥发性有机物方法检出限见表8256。

表8256 共沸蒸馏提取水样中挥发性有机物的方法检出限

续表

色谱图见图8220～图8224。

图8220 300×10-6汽油标准色谱图

图8221 30×10-6柴油标准色谱图

图8222 30×10-6柴油标准色谱图在C10～C18之间的基线

图8223 使用共沸蒸馏法提取试剂水中挥发性化合物色谱图(混合物1)

图8224 使用共沸蒸馏法提取试剂水中挥发性化合物色谱图(混合物2)

注意事项

1)当分析挥发性有机物时，样品在运输和贮存过程中可能被穿过容器隔膜的外界挥发性有机物(尤其是含氯氟烃和二氯甲烷)污染。准备一份纯水作空白样品，使其经过取样和后续的贮存和处理操作过程，用以监测样品污染。

2)高浓度和低浓度试样的连续分析可能导致高浓度试样的残余物对后续低浓度试样的污染。为了降低这种污染，在分析不同试样时必须先用适当的溶剂将进样针或吹扫装置洗净。分析非常规浓度的试样后都应分析溶剂空白，以防止仪器中残留的试样污染后续试样。

3) 清洗器皿时，先用洗涤液洗涤，再用蒸馏水冲洗，接着放置于 105℃ 的烘箱中烘烤。清洗进样针或自动进样器时，用适当的溶剂冲洗沾有试样的表面即可。

所有的玻璃器皿都必须认真的清洗。玻璃器皿尽可能用完后立即用最后使用过的溶剂冲洗，接下来应当用含有洗涤剂的热水洗涤，再用自来水和纯水冲洗。最后晾干玻璃器皿后放置于 130℃烘箱中烘几小时，或用甲醇冲洗后晾干，存放在清洁环境中。

4) 火焰离子化检测器 (FID) 是非选择性检测器，可能存在很多干扰分析的非目标化合物。

参考文献和参考资料

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本章编写人: 耗氧量和生化需氧量测定，刘晓雯 (天津市地矿局测试中心) 。微生物等测定，田来生、齐继祥(中国地质科学院水文地质环境地质研究所) ，有机污染物测定，饶竹 (国家地质实验测试中心) 。