Write down the word.
Read the word out loud several times. This will help you in being able to say and spell it. Try to get to the point where you can say it without looking at a pronunciation or the word.
Separate the word into smaller syllables. For example: pneu-mono-ultra-micro-scopic-silico-volcano-coniosis.
Learn to spell each section, then put them together.
Practice it. Practice spelling the word until you don't have to stop and think about it.
This may take more than one day to achieve. Be patient with it, and results will come out good in the end.
Practice it. Practice it. Practice it. Is the message clear yet?
Start off slow and be patient!
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